1

Index
P-01. Catalyst Characterization: Challenges in Nigeria Opeoluwa O. Fasanya, AishatOsigbesan, Olabode H. Olabimtan, HayatudeenAminu, Abdulazeez R. Isa, Sharafadeen Gbadamosi, Abuba ar I. !usuf and Abdulazeez !. Atta P-02. Bioplastics: Prospects and Opportunities in Nigeria "amido S.I. # Ali A.$. P-03. Reducing Sugar Production by Enzymatic Sacchari ication o Sodium !ydro"ide !ydrogenPero"ide pretreated Sugarcane Bagasse A.O. Ayeni, %.&. Ogue'iofor, F.(. Hymore, ).*. *feo+bo han P-04. #he Nigerian Content $ct as a Springboard or %ndustrial &e'elopment ,ohnson &. Ola'uyigbe P-05. Predicti'e (odeling and &etection o Oil Pipeline )ea*age A.- Orga, *.* *ffiong and *. Awhenu P-06. Production o $cti'ated Carbon rom Sugar Cane Bagasse .%. Salahudeen, -. S. A'inomoh, $. %uhu, S. O. Omaga and -. S. A pa a P-07. E"tension o !eat Pump+!eat Engine Principles to &istillation Column $nalysis Ola unle $. S., Adefila S. S., Olawale A. S. and .uga'e .I $. P-08. Production o Cellulosic Ethanol rom Sa,dust modi ied ,ith $mmonium Sulphate .assey, *. %., Oboh, I. O., ,ohn, A. .. # !esufu, S. O. P-09. Re'ie, o Sa,dust Pretreatment Processes -or Bio uel Production (uye Ayoade, OnuoraO orie and *dem/tibe .enedi0t . P-10. $ Ne, E"plicit (odel or Predicting -riction -actor in a -ully &e'eloped #urbulent Pipe -lo, Offor, /.H.and Alabi, S... P-11. /inetics (odeling by non0linear Regression (ethod or the Sorption o )ead 1%%2 %on onto a Biomaterial Oboh, I. O., Aluyor, *. O., Audu, &. O. (., .assey, *. %.and !esufu, S. O. P-12. Optimization o Natural 3as Pipeline Net,or* 4sing the Combined 3eneralized Reduced 3radient and (ulti0Start (ethod Ambrose %. Anozie, /deme O. *ton P-13. %n'estigation into the Competiti'e %nhibition o !ydrocarbon &egradation in Pond System or 5et Season upon the %n luence o (omentum #rans er / pa a, -. 12 Ogoni, H.A and %nadi, ).G P-14. Petrochemical &e'elopment in Nigeria: #he Need -or Pilot Plants G. ,. Igwe P-15. Simulation and Per ormance $nalysis o Propylene 0 Propane Splitter in Petroleum Re inery Case Study A. $./mo and *. %. .assey P-16. Synthesis o -le"ible Polyurethane -oam using Castor Oil+Polyol as a (onomer Ogunfeyitimi, O. S., O ewale, A.O., Igbo we, 1.(. P-17. #he Role o Catalysis in the &e'elopment o the Petrochemical %ndustry in Nigeria Abdulazeez R. Isa, SharafadeenGbadamosi, Opeoluwa O. Fasanya, Abuba ar I. !usuf, Aishat Osigbesan, Olabode H. Olabimtan, HayatudeenAminu, and Abdulazeez !. Atta.

6 P-18. -unctionalization o 7eolite $ Synthesised rom Nigerian $ho*o /aolin or $dsorption Study o (ethylene Blue Alaya Sherifat and.S. (o+o P-19. Batch Studies on Remo'al o Chromium rom $8ueous Solution using (odi ied Nigeria $ho*o /aolin S.I. Ayilara, A.S. (o+o, Abuba ar, G and A uso, S.A P-20. Strategy or Balancing Petroleum %ndustry $cti'ities and Biodi'ersity Conser'ation: $n $ssessment o Biodi'ersity E"ploitation in the Stubbs Cree* -orest Reser'e9 $*,a %bom State9 Nigeria ,oshua &. %doho P-21. E ect o Particle Size and #emperature :ariation on the ;ield o Essential Oil rom )emon 3rass using Steam &istillation *.&.A hihiero and ..).Ayodele P-22. /inetics and %sotherm Studies o Pb1%%2 $dsorption on %*poba Clay /wadiae, S. *., Aluyor, *.O., O ieimen, -.O and Oboh, I.O.

P-01 Catalyst Characterization: Challenges in Nigeria

Opeoluwa O. Fasanya*, Aishat Osigbesan, Olabode H. Olabimtan, Hayatudeen Aminu, Abdulazeez R. Isa, Sharafadeen Gbadamosi, Abubakar I. Yusuf, Abdulazeez Y. Atta National Research Institute for Chemical Technology, Zaria * opefas@gmail.com; ope.fasanya@narict.gov.ng

Abstract
The petroleum industry is the mainstay of Nigerias economy. Catalysts play an integral role in not just the petroleum refining process but about 90% of chemical processes such as pollution control, production of chemicals and renewable energy. The science and applications of catalysis is therefore a must for development of the process industry. Catalyst characterization is required for the design and testing of catalysts. This requires the use of analytical equipment to determine the properties of a catalyst so as to improve its properties and operation. There is a lack of analytical equipment for catalyst characterization in Nigeria. This paper highlights the problems faced by researchers in the field and proffer possible solutions.

Introduction
Catalysts are a major part of the chemical process industry. They are not just an integral part of chemical process technology but can be said to be a central technology for improving the quality of life and a sustainable future (Centi, et al., 2002). Production of Catalysts and the development of the science of catalysis are significant to the progressive development of any economy.About 80% to over 90% of chemical processes utilizes catalysts in one form or the other (Marcilly, 2003; Centi & Perathoner, 2008). The research and development in catalysts science and technology is important for any nation that seeks to be classified as a developed nation. Petroleum refining, petrochemicals production, renewable energy, pollution control, water purification and the production of specialty chemicals are a few fields of interest in Nigeria which require the application of catalysts. The importance of catalysis to energy, economic and environmental security cannot be overemphasized especially in Nigeria where the petroleum industry is the anchor of the

economy. Virtually every major refining process utilizes catalysts. Improved catalytic processes therefore will lower energy requirements, make better use of natural resources, reduce formation of unwanted by-products and eliminate contaminant effluents (Martinez & Corma, 2011). This will result in increased profitability and better environmental protection. A survey in the united states of America between 1998 and 2002, showed the world market for catalysts was about 9 billion US dollars (Centi, et al., 2002, Armor, 2011) with the demand forecasted by the Freedonia group to grow to about 16.3 billion US dollars as of 2012(Armor, 2011). Catalysts used by major industries in Nigeria are all imported. A huge amount of savings can be made from the production of catalysts locally using locally sourced raw materials. Nigeria is also blessed with local raw materials such as kaolin, silica, etc. which can be utilized for catalyst production. Nigeria has over 40 recorded occurrences and deposits of kaolin clay (Ekosse, 2010) which can be used for the production of zeolite. Various researchers have already carried out work on local kaolin deposits for zeolite production which is the main catalysts in refinery and petrochemical industry (Atta, et al., 2012). A challenge that impedes progress is catalyst characterization. Most key analytical equipment required for catalysts characterization are either not available or not functioning properly. Various governments have recognized the importance and the need for catalysis research and have instituted policies to ensure that catalysis research thrives in their countries. Table 1 shows some research institutes that focus on catalysis, around the world. Table 1: Some Catalysis Research Centres in the World
Location Name Year Established Netherlands Netherlands Institute for Catalysis research 1991 Northern Ireland Centre for Theory and Application of Catalysis Unknown America Catalysis Centre for basic and applied research - Oak Ridge national laboratory Unknown South Africa University of Cape Town Centre for Catalysis Research Unknown Centre for Catalysis research University of Johannesburg Unknown DST/NRF Centre of excellence in catalysis, South Africa Unknown Sweden Competence Centre for Catalysis 1995 Japan Hokkaido University Catalysis research centre 1943 Ottawa Canada Centre for catalysis research and innovation 2000 India National centre for catalysis research, Institute of Technology Madras 2006 Germany TUM Catalysis Research Centre Unknown Leibniz institute for catalysis 2006 Saudi Arabia KAUST Catalysis centre 2010

From Table 1, it will be seen that even countries like South Africa have recognized the need for catalysis research and have established at least 3 research centers for this purpose. The list presented in table 1 is by no means exhaustive but serves to present a glimpse of catalysis research interests around the world. A perceived common factor amongst all the institutes listed above is the backing and support of their respective federal governments and funding by private industries and organizations. This creates an enabling environment for productive research and development. This paper attempts to briefly explain the importance of catalysts characterization, look at some common characterization techniques and the challenges faced by Nigerian researchers.

Catalyst Characterization
An integral part of the science of catalysis is catalyst characterization. Catalysis as a whole comprises the varieties of heterogeneous, homogeneous and biological catalysis (Cornils & Hermann, 2003).The main focus of this paper is on characterization of heterogeneous catalysts. The most remarkable difference between catalysis during the 1950s and nowadays is the development of characterization techniques. As scientists, research into catalyst composition, structure of framework of solid and the nature of its porosity are essential parameters to correlate with catalyst performance. Characterization allows for identification of properties that discriminate between poor and successful catalysts. Table 2 shows methods used for analyzing the different properties of a catalyst. Major Characterization techniques include X-Ray Diffraction (XRD), X-Ray Photoelectronic Spectrometer (XPS), Temperature Programming techniques, Infrared, Transmission Electron Microscopy (TEM), and Scanning Electron Microscopy (SEM) Table 2: Methods for Analyzing Various Catalyst Properties
Property Method Composition XPS, XRF, XRD, ICP, AAS Particle size Electron microscopy, BET, optical microscopy, TEM Structure XRD, XPS, , TEM, FTIR, AFM, STM Degree of reduction TPR, XPS, XANES Surface area BET Morphology TEM, SEM, AFM, STM

Many techniques are available for solid examination of materials but not all are appropriate for the study of real catalysts. Some of these techniques could result in a change in the nature of the sample therefore it is essential that characterization techniques are chosen carefully with full knowledge of the problems associated with each technique. These techniques require special expertise in the interpretation of results (Haber, et al., 1995). Brief descriptions of some common techniques are given in this section; Brunauer-Emmet-Teller (BET): is a physical adsorption process (Aslani, et al., 2013; Leofanti, et al., 1997). Adsorption methods are used to provide information about the total surface area of the catalyst, the surface area of the phase carrying active sites, or possibly even the number of active sites. BET utilizes physical adsorption to determine the total surface area of the catalyst particles.This method expresses the relationship between the total surface of the catalyst and the weight of the same one and usually is expressed in m2/g (meters squared of surface on gram of catalyst). Other properties such as particle and pore sizes distributions can be obtained.

Scanning Electron Microscopy (SEM): This technique is used to study the microstructural characteristics of solid materials. Its application extends to images within the size range of 25 to 50. Using SEM it is possible to obtain 3 dimensional images due to a greater depth of field. The applications of SEM in catalyst characterization; especially the analysis of our locally sourced clays are enormous. The first real SEM was developed by Zworykin in 1942. (Kovo, 2011) Transmission Electron Microscopy (TEM): provides structural information on catalysts, direct images of surfaces and elemental composition and distribution. It is suitable for examination of supported catalysts with particle sizes down to 2-3nm, giving information on particle location over the support, particle-size distributions, particle and support morphology and the nature and distribution of deposits having thickness of the order of 23nm. (Leofanti, et al., 1997) High Resolution Electron Microscopy (HREM): provides information on local crystallinity and can show up the overall morphology and surface structure that may be present in the supported metal catalyst systems. It is often the only technique capable of providing accurate information on stacking faults and other crystal defects that may play a critical role in defining catalysts properties (Crozier & McCartney, 1996) X-Ray Diffraction (XRD): is one of the most important techniques for catalyst characterization. For most catalysts, XRD is limited to powder-pattern identification of crystalline phases. For zeolites and catalysts with good crystallinity, long range order exists, and XRD can give a complete description of their structure (Leofanti, et al., 1997). X-Ray Fluorescence (XRF): is a non-destructive technique used for multi-element analysis. It allows for determination of several elements in solid or liquid states with high sensitivities. It is effective for analysis of major and trace elements in ceramics, metals and rocks (Kovo, 2011). X-Ray Photoelectron Spectroscopy (XPS): is a widely used surface analysis tool for heterogeneous catalysts because of its simplicity in use and data interpretation and its suitability to all solid samples (Fadley, 1978;Weng, 2013). Photoelectron spectroscopy involves exposing the specimen to be studied to a flux of nearly monoenergetic radiation radiation with mean energy and then observing the resultant emission of photoelectron. Nuclear Magnetic Resonance (NMR): It is an indispensable tool for the identification and chemical structural analysis of various materials. It was discovered sixty five years ago (Nakata, et al., 1998). Analysis can be carried out on solids without the need for dissolving in solvents and without being destroyed so that chemical information peculiar to each solid can be obtained as it is in the solid state. Scanning Near-Field Optical Microscope (SNOM): This is one of the most recent developments in the field of spectroscopy. SNOM is a proximal probe technology that allows optical excitation of materials at spatial resolutions well below the diffraction limit and has become a powerful tool for nanofabrication and catalyst characterization. (Tseng, 2007)

Equipment and Challenges in Nigeria

Access to equipment for catalysis characterization is one of the major challenges of catalysis research in Nigeria. Challenges include: availability of equipment, location of these equipment, quality and maintenance culture of the equipment, technical knowhow of

researchers and technologists, lack of analytical standards and lack of constant power supply. Table 3 gives an overview of some equipment available for catalyst characterization in certain locations of the country. Ascertaining the working conditions of the equipment in table 3 was not possible during the preparation of this paper. Table 3: Some Characterization Equipment in Nigeria S/N Equipment Location in Nigeria
1 Brunauer-Emmet-Teller (BET) Surface Area

Analyzer
NARICT, Zaria 2 Scanning Electron Microscope (SEM) A.B.U, Zaria , SHESTCO Abuja, Kastina State University, Katsina 3 Transmission Electron Microscope (TEM) FUT Minna, SHETSCO Abuja 4 Gas Chromatography Mass Spectrometer (GC-MS) NARICT, Zaria, University of Ilorin, Ilorin Usman Danfodio University, Sokoto 5 Fourier Transform Infra Red Spectrometer (FTIR) Readily available 6 X-Ray Diffraction (XRD) National Geosciences Research Laboratory Kaduna, National Steel Council Kaduna, DICON, Kaduna 7 X-Ray Fluorescence Spectrometer (XRF) SHESTCO Abuja, National Geosciences Research Laboratory Kaduna, 8 Micro Reactivity Reactor Not Available 9 X-Ray Photoelectronic Spectrometer (XPS)

Not available
10 Nuclear Magnetic Resonance (NMR) NARICT, Zaria, OAU, Ile-Ife.

Whilst the table 3 does not fully capture the list of analytical equipment in Nigeria, it does show the challenges that researchers have in accessing information about equipment for research. It shows the distances that some researchers have to travel in order to test samples. It also goes ahead to show the long waiting times that will be required by researchers in order to get their samples analyzed. The quality of some equipment available is also questionable. Rather than going for renowned and trusted brands; based on our observation; the culture is the acquisition of substandard products with no guarantee from unknown manufacturers. This results in lack of

training or maintenance of the equipment by the manufacturers since no manufacturer was identified. A lot of equipment can be found laying around that fit this description. To prevent this, the method of equipment procurement should be checked to ensure that certified equipment are brought into Nigerian laboratories. In an ideal situation, manufacturers or their representatives should be available to maintain or train staff on the equipment supplied by their companies. The training of researchers and technologist in the use of equipment which many have not been exposed to is a must. Due to the few number of equipment available, only a handful of researchers have had one on one contact with these equipment. This has led to cases wherein only technical staff and technologists being allowed to run equipment and students and other researchers not fully understanding how these machines work. Access to these equipment will invariably expand the mind of the researcher as to various applications and ways the equipment can be used for positive research. For many analytical equipment and experimental procedures, constant power supply is a must; else improper shutdown could lead to damaging components of the equipment. There are also analyses which require long periods of time for completion wherein any interruption in power supply would result in failed analysis (Tasfy, et al., 2011).

Conclusion
It has been established that characterization of catalysts is important for meaningful catalysis research. The use of catalysts by our petroleum and refining industries are not the only reason for the Nigerian government to invest in the development of catalysis research. The immense environmental applications are equally important reasons which should necessitate investment and support in the area. The work of local researchers in this field will progress faster to the advantage of the country if the government will recognize the need for, and support, catalysis research in Nigeria. Establishment of an institute for catalysis research equipped with fully functional state of the art analytical equipment will be beneficial in the development of catalysis research in Nigeria. Subsequently, at least one university or research institute in each of the 6 geopolitical zones should have a centre of excellence of catalysis research. These centers should be equipped with analytical equipment of high quality and staff that are competently trained in their use and certified to train others. An annual conference on catalysis research in Nigeria which should subsequently birth a journal of Nigerian catalysis developments should also be considered.

References
Armor, J. N., 2011. A history of industrial catalysis. Catalysis Today, Volume 163, pp. 3-9. Aslani, A., Arefi, M., Beyki-Shuraki, K. & Babapoor, A., 2013. Direct syntheses, characterization adn optical analysis of PbX2 (X=1,Br and Cl) nanoparticles without any additives. Journal of Saudi Chemical Society, Issue 17, pp. 403-407. Centi, G., Ciambelli, P., Perathoner, S. & Russo, P., 2002. Environmental catalysis: trends and outlook. Catalysis Today, Volume 75, pp. 3-15. Centi, G. & Perathoner, S., 2008. Catalysis, a driver for sustainability and societal challenges. Catalysis Today, Volume 138, pp. 69-76. Cornils, B. & Hermann, W. A., 2003. Concepts in homogeneous catalysis: the industrial view. Journal of catalysis, Issue 216, pp. 23-31.

Crozier, P. & McCartney, M., 1996. Elemental Mapping of Heterogeneous Catalysts by Energy-Filtered Transmission Electron Microscopy. Journal of Catalysis, Issue 163, pp. 245254. Degnan Jr, T. F., 2007. Recent progress in the development of zeolitic catalysts for the petroleum refining and petrochemical manufacturing industries. s.l., Elsevier. Ekosse, G.-I., 2010. Kaolin deposits and occurences in Africa: Geology, minerology and utilization. Applied Clay Science, Issue 50, pp. 212-236. Haber, J., Block, J. & Delmon, B., 1995. Manual of methods and procedures for catalyst characterization (Technical Report). Pure & Appl. Chem, 67(8/9), pp. 1257-1306. Kovo, A. S., 2011. Development of zeolites from zeolite membranes from Ahoko Nigerian Kaolin. s.l.:PhD Thesis submitted to The University of Manchester. Leofanti, G. et al., 1997. Catalyst Characterization:characterization techniques. Catalysis Today, Issue 34, pp. 307-327. Marcilly, C., 2003. Present status and future trends in catalysis for refining and petrochemicals. Journal of catalysis, Volume 216, pp. 47-62. Martinez, C. & Corma, A., 2011. Inorganic molecular sieves: Preparation, modification and industrial application. Coordination chemistry reviews, Issue 255, pp. 1558-1580. Nakata, S., Tanaka, Y., Asaoka, S. & Nakamura, M., 1998. Recent advances in applications of multinuclear solid-state NMR to heterogeneous catalysis and inorganic materials. Journal of Molecular Structure, Issue 441, pp. 267-281. Pawelec, B. & Fierro, J., n.d. Characterization of catalysts: Bulk and Texture. In: Encyclopedia of life support systems. s.l.:s.n. Tasfy, S. F. H., Zabidi, N. A. M., Subbarao & Duvvuri, 2011. Performance Characterization of Supported Iron Nanocatalysts for Fischer-Tropsch Synthesis. Journal of Materials Science and Engineering A, Issue 1, pp. 9-15. Tseng, A. A., 2007. Recent developments in nanofabrication using scanning near-field optical microscope lithography. Optics and Laser Technology, 39(3), pp. 514-526. Weng, L.-T., 2013. Advances in the surface characterization of heterogeneous catalysts using ToF-SIMS. Applied Catalysis A: General, p. Article In Press.

P-02 BIOPLASTICS: PROSPECTS AND OPPORTUNITIES IN NIGERIA Lamido, S.I. (chemicalsanee@g.mail.com) and Ali, A.M. (abubakarali2004@yahoo.com) Department of Chemical Engineering, Kaduna Polytechnic, Kaduna, Nigeria Abstract Plastics are a vital asset for humanity, often providing functionality which cannot be easily or economically replaced by other materials. Oil and natural gas are the major raw materials used to manufacture most plastics. Replacing petroleum-based plastics with plastics made from renewable raw materials, such as plants, reduces our dependence on fossil fuels. Replacing petroleum-based plastics with plastics designed to degrade, biodegrade, or compost can provide even more environmental benefits. Biobased and compostable plastics, also known as bioplastics, hold the potential to reduce dependence on fossil fuels, foster the development of more sustainable products, and increase the diversion of food waste from landfills. Keywords: Plastic, Bioplastic, Biobased, Biodegradable, Compostible, Biomass, Waste. Introduction Plastic is the most versatile synthetic manmade substance, created out of the fossil fuel resources. Plastic offer a number of advantages over alternative materials they are lightweight, low cost, extremely durable and relatively unbreakable. Plastics are composed of petroleum based materials called resins (e.g., polythene and polypropylene) materials that are resistant to biodegradation (Chonde et. al., 2010). Plastics belong to a group of molecules called polymers, which are large molecules made of repeating units called monomers. Most plastics contain between 500 and 20,000 or more repeating units (Cynthia, 2010). Despite their numerous advantages, synthetic plastics constitute major environmental and public health problems in Nigeria, particularly in the urban areas. ( David, 2012). A very high percentage of plastic is mostly used for disposal of low value items such as food wrap and product packaging but there is nothing particularly disposable about most plastics. Plastic bags are used

for about 12 minutes before getting rid of them yet they can take 20 - 100years to breakdown in the environment. (Zareena, n.d.). Getting rid of plastic is extremely difficult; burning them can give off toxic fumes. Plastic bag wastes (especially pure water sachet) contribute in the blockage of drains and gutters. Furthermore, when filled with rainwater, plastic bags become breeding ground for mosquitoes, which cause malaria. (Zareena, n.d.) A bioplastic is a plastic that is made partly or wholly from polymers derived from biological sources such as sugar cane, potato starch or the cellulose from trees, straw and cotton. Some bioplastics degrade in the open air, others are made so that they compost in an industrial composting plant, aided by fungi, bacteria and enzymes. (Goodall, 2011). Bio-based and biodegradable plastics can form the basis for environmentally preferable, sustainable alternative to current materials based exclusively on petroleum feed stocks. These bio-based materials offer value in the sustainability/life-cycle equation by being a part of the biological carbon cycle. (Gautam, 2009). Biodegradation is the process in which microorganisms like fungi and bacteria degrade the natural polymers (lignin, cellulose) and synthetic polymers (polyethylene, polystyrene) (Gu, et. al., 2000). As the microorganisms possess different characteristics, so the degradation varies from one microorganism to another. Various factors which are responsible for biodegradation are kind of polymers, organism characteristics, and the type of treatment required (Artham, 2008). Discoloration, phase separation, cracking, erosion and delimitation are some of the characteristics which indicate the degradation of polymers. Breakage of bonds, transformation due to chemicals, and synthesis of new functional groups are responsible for the variations (Himani, et. al., 2012). Bioplastics can be classified as biobased, biodegradable or both. (European Bioplastics, 2012). -Biobased: The term biobased means that the material is (partly) derived from biomass (plants). E.g. corn, sugarcane, or cellulose which are renewable raw materials. - Biodegradable: a plastic derived from renewable biomass that can be broken down in the environment by micro-organisms. There is a common misconception that the terms biobased and biodegradable are interchangeable. Most, but not all, bioplastics can be broken down in the environment by microorganisms (as part of the carbon cycle) in a process called biodegradation. This process produces carbon dioxide (CO2) and water (H2O) under aerobic conditions or methane (CH4) under anaerobic conditions (in the absence of air) such as in landfill. (HGCA, 2009) Mixed bioplastics are usually biodegradable, but some are not and can be either recycled or processed for energy recovery. Notable examples of bioplastics most recently include Coca Colas bio-PET (partially biobased), and Braskems fully biobased polyethylene (PE). Why Bioplastics? About 4% of the worlds oil production is converted into plastics for use in products as varied as shopping bags and the external panels of cars (Goodall, 2011). Another few percent is used in processing industries. Because oil-based plastics require substantial amounts of energy to manufacture, each kilogram of plastic typically requires 20 kilowatt hours of energy in the manufacturing process, more than the amount needed to make steel of the same weight. Almost all this comes from fossil sources (Goodall, 2011 and Terer et. al., 2012). As oil runs out, and the use of fossil fuels becomes increasingly expensive, the need for replacement sources of raw material for the manufacture of vital plastics becomes increasingly urgent. In addition, the use of carbon-based sources of energy for use in plastics manufacturing adds greenhouse gases to the

atmosphere, impeding the worlds attempts to cut CO2 emissions. Nigeria, being oil producing country and with low industries to contribute to the global warming is most threated by the large amount of plastic wastes which constitute a major environmental and public health problems. According to Lagos State Waste Management Authority (LAWMA), Lagos metropolis, like most cities in Nigeria, generates 9,000 metric tonnes per day of solid waste. A recent study carried by the Bayero University Kano Consultancy Unit (March, 2012) estimated the following composition for Polythene/cellophane = 19% Paper = 12.7%, Metal= 10%, Glass=8.7%, Plastics=11.3%, Fines (ash, dust and sand)=12% Miscellaneous =9% while a study by the Basel Convention Coordinating Centre for Africa in 2009 reveals that 70% of all imports were used electronic electrical equipment of which about 30% could be described as E Waste (Iriruaga, 2012). Overall, there are significant benefits in switching from convectional plastics to bioplastics as show in the table 1 below: Table 1: Comparison between Bioplastics and Petroplastics. Bioplastics Petroplastics Renewable Yes or partially No Sustainable Yes No Breakdown in the environment Biodegradable and/or compostable Some degradable by polymer oxidation Polymer range Limited but growing Extensive GHG emission Usually low Relatively high Fossil fuel usage Usually low Relatively high Arable land use Currently low none Source: Home Grown Cereals Authority UK. (HGCA, 2009) Biodegradability & Compostability Bioplastics can take different length of times to totally compost, based on the material and are meant to be composted in commercial composting facility within 90-180 days at higher temperatures. Most existing international standards require biodegradation of 60% within 180 days along with certain other criteria for the resin or product to be called compostable. (Admira, 2010). It is important to make the distinction between degradable, biodegradable and compostable. These terms are often (incorrectly) used interchangeably. Compostable Plastic These are plastics that can undergo degradation by biological processes during composting to yield carbon dioxide, water, inorganic compounds and biomass at a rate consistent with other known compostable materials; leaves no visible, distinguishable or toxic residue (ASTM, 2004). In order for a plastic to be called compostable, three criteria need to be met: 1. Disintegrate - the material is indistinguishable in the compost, that it is not visible and needs to be screened out 2. Eco-toxicity - the biodegradation does not produce any toxic material and the compost can support plant growth. Biodegradable Plastics These are plastics which will degrade from the action of naturally occurring microorganism, such as bacteria, fungi etc. over a period of time. There is no requirement for leaving "no toxic

residue", and as well as no requirement for the time it needs to take to biodegrade. Degradable Plastics These are plastics which will undergo a significant change in its chemical structure under specific environmental conditions resulting in a loss of some properties. Here there is no requirement that the plastic has to be degraded from the action of microorganisms or any of the other criteria required for compostable plastics. A plastic therefore may be degradable but not biodegradable or it may be biodegradable but not compostable (that is, it breaks down too slowly to be called compostable or leaves toxic residue). Table 2 below shows the different time taken for various bioplactics to compost using home composting and commercial composting techniques. Table 2: Estimated Composting Times of different Bioplastic Products Product Home Composting Commercial Composting Sugarcane fiber/Reed Grass: Takeout Containers, Bowls Cups and Trays 2-4 Months 1-3 Months PLA: Cold Cups, Deli containers and Straws 6-12 Months 3-6 Months Corn Starch: Heatresistant, Non-GMO Utensils 12-24 Months 6-18 Months Trash/ Kitchen Bags 3-6 Months 1-3 Months PLA: Testing Spoons and Utensils 12-24 Months 3-6 Months Source: Bioplast (Admira, 2010). It can be seen from table 2 that, the rate of biodegration for different biocompostables is faster in commercial composting due to the additional composting conditions present in it. Types of Bioplastics Starchbased bioplastics Starch-based bioplastics can be manufactured from either raw or modified starch e.g. thermoplastic starch (TPS) or from the fermentation of starch derived sugars e.g.Polylactic acid (PLA). Common starch sources include maize, wheat, potatoes and cassava (Anita, 2011 and HGCA, 2009). Cellulose-based bioplastics Cellulose-based bioplastics are typically chemically-modified plant cellulose materials such as cellulose acetate (CA). Common cellulose sources include wood pulp, hemp and cotton. e.g poly-3-hydroxybutyrate (PHB), polyhydroxyvalerate (PHV) and polyhydroxyhexanoate (PHH) (Anita, 2011 and HGCA, 2009). Polyamide 11 (PA 11) bioplastics These are biopolymer derived from natural oil. It is also known under the trade name Rilsan B, commercialized by Arkoma. PA 11 belongs to the technical polymers family and is

biodegradable. It is used in high-performance applications like automotive fuel lines, pneumatic airbrake tubing, electrical cable sheathing, flexible oil and gas pipes, control fluid umbilical, sports shoes, electronic device components, and catheters. (Anita, 2011 and HGCA, 2009). Benefits of Bioplastics Reduced CO2 Emission: One metric ton of bio-plastics generates between 0.8 and 3.2 fewer metric tons of carbon dioxide than one metric ton of petroleum-based plastics (Anita, 2011). Electronic giant Sony uses PLA in several of its smaller components. Rising oil prices: Bioplastics are becoming more viable with increasing and instability in oil prices, which are in turn triggering spikes in conventional plastic costs, illustrated in a sharp upturn in the past few years. Dwindling oil supplies means that man will eventually be forced to turn to a sustainable basis for plastics. Waste: Bioplastics reduce the amount of toxic run-off generated by the oil-based alternatives but also are more commonly biodegradable. The USs second largest biopolymer producer Metabolic, of Cambridge, Massachusetts, claims that its plastics are biodegradable in composting bins, wetlands and the oceans. Benefits to rural economy: Prices of crops, such as maize, have risen sharply in the wake of global interest in the production of biofuels and bio-plastics, as countries across the world look for alternatives to oil to safeguard the environment and provide energy security. Economics Impact The other advantages of bioplastics would be meaningless if they were expensive to produce. The Mirel bioplastic made by Metabolix is about double the price for an equivalent petroplastic. Ingeo, a bioplastic made by NatureWorks LLC is slightly more expensive than equivalent petroleum based plastics; this is because the companies are based in US where petroleum products and the agricultural feedstock are both expensive. (Brian, 2009). A switch to bioplastics would affect raw material prices. The cost of crop or combination of crops used to make the bioplastics would certainly rise. Increase in corn prices as a result of ethanol production is a good example of this effect. Corn prices have risen dramatically over the past several years as more and more ethanol are produced as an alternative fuel. The prices of bioplastic products, if produced in Nigeria, an oil producing country where there is abundant land for farming, should be expected to compete with the conventional plastics while having an added advantage of being biodegradable. Prices of bioplastics are expected to fall continuously as the industry grows and as more efficient production methods are being developed. Bioplastic and Food Supply The switch to bioplastics has the potential to affect the worlds food supply in number of ways. Bioplastics derived from food crops like corn, soy, sugar cane, e.t.c would directly decrease the amount of those crops that would be available as food. Bioplastics derived from non-food crops like switch-grass would indirectly have a negative impact on food production by competing for land with food crops although Nigeria is blessed with abundant barren land which is yet to be utilized. Food shortages exist in many regions of the world interfering with the worlds food supply is a major concern. Market Opportunities The chemical industry is among the ten largest in the world and currently aims at positioning its self among the top five. In this context, the development of a local bioplastics supply chain will represent an important growth of the chemical industry in Nigeria. The bioplastic market is incipient in Nigeria, where only insignificant volume comes in from import as products with no record of production. As such, for bioplastics market to be established, the following

requirements should be met: Lower bioplastic resin price (greater production capacity) Legislative and financial incentives for using bioplastics Improved disposal infrastructure Greater public awareness of bioplastic materials and how to dispose of them A bioplastic demonstration plant There are many opportunities to be seized, the country has an unbeatable competitive advantage to local production of bioplastics derived chain of agricultural products, since the cost of production and processing of these raw materials in the country is still very low. The market analysis of Helmut Kaiser Corporate Consultants showed that in 2007, 65% of bioplastics were used in the packaging and food related industry. More so, bioplastics has fast market growth of 8-10% per year which is expected to increase in years to come (Helmut, 2012). The results highlight the intermediate trend of the bioplastics. Judging by the statements made, the potential and market opportunities are real. The market chances and the potential are very positive and euphoric. Conclusion Bioplastics are renewable and sustainable alternatives to oil-based plastics. Currently, the main opportunities for bioplastics are in packaging materials, but in future may be used more in higher value applications (electronics and vehicle parts). Bioplastics have a 0.1% share of the current global plastics market. Land usage for the production of bioplastics is currently small (e.g. 0.1% of US maize area for production) but available in Nigeria The world bioplastics market has potential to grow six-fold in years to come. There is the Potential for Agricultural byproducts to be used in bioplastic manufacture. Implementation of the correct disposal methods and corresponding infrastructure are vital if bioplastics industry is to flourish and deliver environmental benefits. References Alexandre, B.,(2010); Bioplastics: Environmental Biodegradable Resins &Additives , ADMIRA LIMITED http://www.bioplast.com.hk/biodeA.htm , accessed on 10 July, 2013 American Chemistry Council (2013), Life Cycle of a Plastic Product. http://www.americanchemistry.com/s_plastics/doc.asp?CID=1571&DID=5972 (accessed April 17, 2013). Anita A. S., (2011), Bio-plastic, Artham T, Doble M (2008); Biodegradation of Aliphatic and Aromatic Polycarbonates, Macromol Biosci 8: 14- 24. Bhardwaj H, Gupta R, Tiwari, A.,(2012) Microbial Population Associated With Plastic Degradation. School of Biotechnology, Rajiv Gandhi Proudyogiki Vishwavidyalaya, Bhopal (M.P), India Retrived from: http://dx.doi.org/10.4172/scientificreports.272 ASTM, (2004), Standard Specification for Compostable Plastics, ASTM International, West Conshohocken, PA, 2004, DOI: 10.1520/D6400-04 Babayemi, J., and Dauda, K., (2009); Evaluation of Solid Waste Generation, Categories and Disposal Options in Developing Countries: A Case Study of Nigeria, Department of Chemical Sciences, Bells University of Technology, Km 8, Idiroko Road, Benja Village, Ota, Ogun State. Barry E., (2009); Biobased Performance Bioplastic: Chemistry & Biology Innovation, Elsevier, DOI 10.1016/j.chembiol.2009.01.001

Biopolymers in the Existing Post consumer Plastics Recycling Stream http://www.springerlink.com/content/h861m8705632h010/ retrieved 10 th August, 2013. Bioplastic Industry; National Innovation Agency (NIA) 2012; 73/1 Rama VI Road, Rajdhevee, Bangkok 10400 Thailand.http://www.nia.or.th. 10th August, 2013. Brian M., (2009); Assessment of the Impacts of Bioplastics: Energy Usage, Fossil Fuel Usage, Pollution, Health Effects, Effects on the Food Supply, and Economic Effects Compared to Petroleum Based Plastics, Worcester Polytechnic Institute, England. 4-11 Chonde Sonal, Chonde Sachin. Bhosale, P., Nakade D., Raut P., (2012); Studies on Degradation of Synthetic Polymer Nylon-6 by Fungus Trametes versicolor NCIM 1086, International Journal of Environmental Sciences, Integrated Publishing Association, Volume 2, No 3. 2435-2439 ISSN 0976 4402, doi: 10.6088/ijes.00202030124 Cynthia, W.,(2010); Plastics go Green, Chemmatters, http://www.acs.org/chemmatters/plasticsgogreen.htm. Accessed on: 6th August, 2013. David, J. I., (2012); The Environmental threat of Sachet Water Package (Waste) on Agricultural land: Conference on Agriculture, Chemical and Environmental Sciences (ICACES'2012) Oct. 6-7, 2012 Dubai (UAE) European Bioplastics (2012), Bioplastics at a Glance, Marienstrasse 19-20 10117 Berlin, Germany. http://www.european\bioplastics.org/index.php?id=182(accessed on12 July, 2013). Gautam, S. P., (2009), Biodegradable Plastics: Impact on Environment, Central Pollution Control Board, Ministry of Environment and Forest, India. 6-14. Goodall C., (2011): Bioplastics; an Important Component of Global Sustainability. White paper, UK. . http://www.carconcommentary.com/2011/09/02/2061 (accessed on 4th April, 2013). Gu, J. D., Ford, T. E., Mitton, D.B., Mitchell, R., (2000); Microbial degradation and deterioration of polymeric materials, Revie RW (eds) In: Uhlig Corrosion Handbook. (2nd ed.) John Wiley & Sons, New York. Harald, K., (2005); Highlights in Bioplastics, IBWA, International Biodegradable Polymers Association & Working Groups Marienstrasse 19/20D-10117 Berlin Helmut, K.,(2012), Bioplastics Market worldwide, Helmut Kaiser Corporate Consultants, http//: www.hkc22.com/bioplastics.html. Accessed on 17th October, 2013. HGCA,(2009), Industrial uses for crops: markets for bioplastics , Stoneleigh Park, Kenilworth,Warwickshire CV8 2TL, retrieved from:www.hgca.com Himani, B., Richa, G., and Archana, T., (2012); Microbial Population Associated With Plastic Degradation, Open Access Scientific Reports, Rajiv Gandhi Proudyogiki Vishwavidyalaya, Bhopal (M.P), India. Retrieved from: http:// doi:10.4172/scientificreports.272 Iriruaga, E. T., (2012): Solid Waste Management in Nigeria, D-Waste Management for Everyone. http://www.d-wasre-management.com/presentations/solid-waste-management-innigeria. html (Accessed on 19th March, 2013). Imoh E. U., and Emmanuel P. U., (2011);Domestic Solid Waste Management in a Rapidly Growing Nigerian City of Uyo, Department of Geography and Regional Planning, University of Uyo, Akwa Ibom State, Nigeria, 36(3): 229-235 Kolybaba, M., Tabil, L., Panigrahi, S.,Crerar, W., Powell, T., and Wang, B., (2003); Biodegradable Polymers: Past, Present, and Future, Department of Agricultural and Bio resource Engineering University of Saskatchewan 57 Campus Drive, Saskatoon, SK, CANADA S7N 5A9, An ASAE Meeting Presentation, RRV03-0007

Narayan, R., (2011); The Science behind Compostable Plastics and the ASTM Standards, Lecture, 2011 US Composting Council Conference, Santa Clara, CA Oliver, W.,Martin P., Manuela, C.,Frank, M., Joachim S.,Brbel, H., Gerhard, A.,(2005); Techno-economic Feasibility of Large-scale Production of Bio-based Polymers in Europ e, European Commission, Joint Research Centre, Institute for Prospective Technological Studies Inca Garcilaso s/n - 41092 Sevilla Spain, EUR 22103 EN Ogwo P.A., Obasi L.O., Okoroigwe D.S. and Dibia N.O, (2013); FROM PLASTIC BAG WASTES TO WEALTH: A CASE STUDY OF ABIA STATE UNIVERSITY, NIGERIA, Journal of Environmental Management and Safety 4, 1, 35 39 Terer, E. K., and Magut, H.,(2012), A Blend of Green Algae and Sweet Potato Starch as aPotential Source of Bioplastic Production and Its Significance to the Polymer Industry , International Journal of Green and Herbal Chemistry,Baraton, Vol.2, No.1, E-ISSN: 2278-3229, Eldoret KENYA. 15-19 Zareena, B., (n.d.), Plastics and environment, Dissemination paper 12, Centre of Excellence in Environmental Economics, Madras School of Economics India. Retrieved from http://coe.mse.ac.in

P-03 Reducing sugars production by enzymatic saccharification of sodium hydroxidehydrogen peroxide pretreated sugarcane bagasse A.O. Ayenia*, N.T. Oguejiofora, F.K. Hymorea, V.E. Efeovbokhana aDepartment of Chemical Engineering, Covenant University, Canaan land Ota, Nigeria

*Corresponding author. Tel.: +23408055745627. E-mail address: augustine.ayeni@covenantuniversity.edu.ng, ayeni_niyi@yahoo.com ABSTRACT The selection of appropriate pretreatment technology and the pretreatment parameters is important for efficient convertion of lignocellulosic materials to reducing sugar by the action of enzymes on the treated biomass. In this study, reducing sugar production from sodium hydroxide-hydrogen peroxide pretreated sugar cane bagasse was optimized using a 2 3-central composite design (CCD) of experiments. The investigation was based on the influences of process parameters of temperature, time, and hydrogen peroxide concentration on the production of reducing sugars after enzymatic hydrolysis process on treated biomass. An optimum pretreatment conditions of 63 oC, 8.5 h, and 3% H2O2 was predicted and experimentally validated to give a reducing sugar yield of 194.75 mg glucose equivalent/g dry substrate. The pretreatment method used in this study showed to have a disrupting effect on the raw material thereby increasing enzymatic action on the treated material to the production of reducing sugars. Keywords: Pretreatment, sugarcane bagasse, Saccharum officinarium, central composite INTRODUCTION Due to environmental concerns, during the last years there has been an increased interest in using ethanol as a transportation fuel. Lignocellulosic materials are attractive feedstocks for ethanol production since they are abundant and cheap (Wheals et al., 1999). One of the major lignocellulosic materials to be considered in tropical countries is sugarcane bagasse, the fibrous residue obtained after extracting the juice from sugar cane ( Saccharum officinarum) in the sugar production process. Sugarcane was introduced into Nigeria in the 15th century for the purpose of chewing and feeding cattles (Iwo and Hussaini, 2001). However, lately, sugarcane has found more uses. Iwo and Hussaini (2001) reported the level of sugar production from sugarcane to be about 170,000 metric tonnes annually. Sugarcane bagasse is rich in carbohydrates (hemicellulose, cellulose, and lignin) but low in nutrients (Zhihong and Holtzapple, 2010). Lignocellulose provides an abundant renewable resource for production of biofuels, chemicals, and polymers (Lynd et al. 2008). Commodities produced from renewable resources offer an alternative to products based on dwindling supplies of petroleum and permit a move towards improved energy security and decreased impact on the environment. Lignocellulosic feed-stocks include residues from agriculture and forestry, energy crops, and residues from bio-refineries and pulp mills. Lignocellulosic biomass can contribute significantly to the future global energy supply without competition with increasing food demand for existing arable land (Metzger and Httermann, 2009). The largest potential feedstock for fuel ethanol is lignocellulosic biomass (Kim and Dale, 2004). Ethanol production from such material can be an attractive alternative to conventional substrates (Wyman, 2001). Cellulose, hemicelluloses, and lignin which are the major components in lignocellulosic materials are bonded together by covalent bonding, various intermolecular bridges, and van der Waals forces forming a complex structure, making it resistant to enzymatic hydrolysis and insoluble in water (OSullivan 1997). Therefore, an efficient, less energy intensive and cost effective pretreatment method is a necessity for producing ethanol at economically viable cost. Pretreatment of biomass is a crucial step to overcome lignocelluloses recalcitrance in the conversion to ethanol (Ayeni et al. 2013). Processes for bioconversion of lignocellulosic materials have been studied extensively. Examples include comminution, irradiation, steam explosion, hydrothermolysis, dilute acid, alkali, solvents, ammonia, SO2, CO2, and other chemicals (Hsu, 1996, Ayeni et al, 2013) Hydrogen peroxide and alkaline oxidative pretreatment (alkaline peroxide oxidation (APO)) is

known to decrystallize cellulose (Gould, 1984). The APO process (an alternative oxidative treatment to air or oxygen delignification) has been shown to be effective in increasing the enzymatic digestibility of crop residues (Gould, 1984). Extensive studies exist on the APO process pretreatment of agricultural residues (Gould, 1985, Saha and Cotta, 2006, Saha and Cotta, 2007. In this study, APO pretreatment of sugarcane bagasse was evaluated with respect to separating the material to its different components. The optimization of enzymatic digestibility of treated solid fraction into reducing sugars was also evaluated with the design of experiments method. 2. MATERIAL AND METHODS 2.1. Raw material Sugarcane was purchased from an open market in late November, 2012 from Zaria Town, Kaduna State, Northern Nigeria. The juice was extracted from the sugarcane stalks at a local mill in Ota, Ogun state, Nigeria. The bagasse obtained was air-dried in an open space for three days (about 8 h per day). Milling was carried out on the air-dried bagasse for size reduction. The bagasse was screened into different size particles using a sieve shaker. The size distribution showed that the particles sizes varied between 0.10 and 1.00 mm. After screening, the samples were manually mixed together with hands for 15 min. The mixed samples were dried in a convection oven at 105 oC for 3 h to a dry matter content of 85% of dry raw biomass. The dried materials were stored in plastic bottles capped tightly and kept at room temperature. The materials were used shortly after. 2.2. Analysis of the raw material Compositional analysis on the raw samples are as previously described by Ayeni et al. (2013). The dry solid content was analyzed by a convection oven. Extractives were determined by means of the Soxhlet extractor on 2.5 g of dry biomass. The Soxhlet extractor was set up with the boiling flask immersed into a water bath set at 70 oC. The siphon period was maintained at 23 min for 4 h. At the end of each extraction periods, the samples were air dried for few minutes at room temperature and further dried at 105 oC in a convection oven. The extractives content was calculated as the difference in weight between the raw and extracted material (Li et al.,2004, Lin et al., 2010). Mineral components were determined by ashing at 575 oC for 6 h. The hemicellulose content was determined by placing 1 g of dried biomass from the extractive analysis into a 250 mL Erlenmeyer flask and then 150 mL of 500 mol m -3 NaOH solution was added. The mixture was boiled for 3.5 h with distilled water. The residue was dried to a constant weight at 105 oC and later cooled in a desiccator and weighed. The hemicelluloses content was obtained as the difference between the sample weight before and after this treatment. Lignin composition was determined by weighing into glass test tubes 300 mg of dry extracted biomass and adding 3 mL of 72% H2SO4. Acid hydrolysis was made to occur by keeping the samples at room temperature for 2 h with mixing of samples every 30 min. 84 mL of distilled water was added to each test tube after the 2 h acid hydrolysis step bringing the total volume to 87 mL. The samples were autoclaved for 1 h at 121 oC. After the second weak acid hydrolysis step, the hydrolyzates were cooled to room temperature and filtered through vacuum using a filtering crucible. The acid insoluble lignin was determined by drying the residue at 105 oC and accounting for ash by incinerating the hydrolyzed samples at 575 oC in a muffle furnace. The acid soluble lignin fraction was determined by measuring the absorbance of the acid hydrolyzed samples at 320 nm (Sluiter et al, 2008). The cellulose content was calculated by difference, assuming that extractives, hemicellulose, lignin, ash, and cellulose are the only components of

the entire biomass (Blasi, et al. 1999). The composition of the sugar cane bagasse used in this study was ash content: 3.70%, extractives: 2.16%, hemicellulose: 34.69%, lignin: 24.84%, and cellulose: 34.61%. 2.3. Statistical design of experiments A statistical 23-central composite design (CCD) was used for the design of experiments (Montgomery, 2001, Mathews, 2005). Table 1 shows the low and high levels of the design. The CCD design was made up of 20 base runs (8 cube points, 4 centre points in cube, 6 axial points, and 2 centre points in axial, 2 base block (Table 2), all in duplicate, resulting in a total of 40 experiments. The objective was to evaluate the influence of reaction temperature (X 1), pretreatment time (X2), and hydrogen peroxide concentration (X 3) on the APO process such that the cellulose content, the hemicellulose solubilization, and delignification will enhance enzymatic hydrolysis of treated materials to reducing sugars. They were chosen for study as these parameters can influence the fractionation of the solid material. Temperature, Time, and oxidation have been reported to have profound effects on ligno-cellulosic materials pretreatment (Ayeni, et al., 2013). Hydrogen peroxide concentration and loading were maintained at constant levels throughout the pretreatments. MINITAB 15 statistical software (Pennsylvania, USA) was used for the design of the pretreatments. The order in which the experiments were carried out was randomized. Table 1. 23- Central composite design of experiments Factors Low level High level Temperature, X1 (oC) 50 70 Time, X2 (h) 4 8 H2O2, X3 (%v/v) 1 3 2.4. Raw material pretreatment The pretreatments were carried out in 500 ml conical flasks. The pretreatment mixtures were heated on magnetic stirrers. 5 g of the dry biomass were mixed with 100 ml of distilled water containing 30%(w/v) H2O2 (0.37%, 1.00%, 2.00%, 3.00%, and 3.63%) and adjusted to pH of 11.5 with respective sodium hydroxide loadings. Slurries were pretreated at different reaction temperature, and time intervals. After each specified time, reaction was terminated by allowing the pretreated slurry to cool at ambient temperature. The pretreated slurry was separated into the solid and liquid fractions by vacuum filtration, and the solid fraction was washed with water. The solid fraction was dried and weighed. The pretreated solid fractions were used to determine the extent of enzymatic hydrolysis and the optimum reducing sugars yield. 2.5. Enzymatic hydrolysis of washed pretreated biomass The pretreated washed solid fractions were hydrolyzed by enzymes to determine the efficiency of substrate conversion. Enzymatic conversion was performed at 2% dry substrate (20 g kg -1 dry biomass content). Sodium citrate buffer (5 mL, 0.1 M, pH 4.8),was added to the wet materials in 50 mL culture tubes. A commercial preparation of Trichoderma reesei cellulase enzyme system with an activity of 57.8 filter paper unit (FPU) mL-1 was added at a loading of 25 filter paper unit g-1 dry biomass. An appropriate volume of distilled water was added to bring the total volume to 10 mL. The progress of the reaction was measured by removing 0.5 mL aliquot at hydrolysis period of 72 h. Experiments were conducted at 50 oC in a non-shaking incubator. To quench the hydrolysis, the samples were boiled for 15 min and then cooled in an ice bath. After hydrolysis, the samples were centrifuged at 4000 revolution min-1 for 5 min to remove residual solids. Fermentable sugars were estimated as reducing sugars with 3,5, dinitrosalicylic acid method (Miller, 1959). The amount of reducing sugars (RS) was calculated as follows (Ma et al., 2010);

Reducing sugars yield from enzymatic hydrolysis (mg equivalent glucose per g dry substrate) = amount of reducing sugar produced after hydrolysis amount of dry biomass (1) 2.6. Statistical analysis of enzymatic hydrolysis The three variables chosen were designated as X1 (Temperature), X2 (Time), X3 (% H2O2). The model generated as a function of these variables on the predicted response of the reducing sugars is a second-order polynomial and is represented as follows: Y = _ + _ _ + + ! ! + _,_ _ + , + !,! ! + _, _ + _,! _ ! + ,! ! (2) The predicted responses are designated as Y (reducing sugars) associated with each factor level combinations; _ to ,! are coefficients to be estimated from regression, they represent the linear, quadratic and cross-products of X1, X2, X3 on the responses; X1, X2, X3 are the factors. The statistical software package MINITAB 15 (PA, USA) was used for regression analysis of experimental data, plotting of response surfaces and to optimize the process parameters. The coefficients in the second-order polynomial (Eq. 2) were calculated by multiple regression analysis, based on the experimentally obtained data, and then the predicted responses were obtained using Eq. (2). Analysis of variance (ANOVA) was used to estimate statistical parameters. 3. RESULTS AND DISCUSSIONS 3.1. Saccharification of pretreated material Enzymatic hydrolysis is used to evaluate the maximum amount of reducing sugars that can be released from the pretreated biomass. The reducing sugars yield is defined as the total sugars yield (as measured glucose) from the enzymatic hydrolysis of the pretreated biomass. The experimental and predicted reducing sugars yields after the 72 h period are given in Table 2. The results indicate that the reducing sugars yields from the pretreatment of the raw sugar cane bagasse after 72 h enzymatic hydrolysis process varied from the minimum of 85.23 mg/g dry substrate to a maximum of 184.2 mg/g dry biomass. Under the experimental conditions investigated in this study, the enzymatic hydrolysis results did not follow a particular trend. However, in general, pretreatments at high temperatures, longer time, and a high H2O2 concentration (greater than or equal to 2) conditions favoured the production of the reducing sugars. In addition, a lower hydrogen peroxide concentration produced smaller amounts of the reducing sugars. For example, at 70 oC, 8 h, and 3% H2O2, the reducing sugars yield was at a maximum (184.2 mg/g) while at 50 oC, 8 h, and 1%H2O2 produced 123.69 mg/g dry substrate. 3.2. Optimization and validation of enzymatic hydrolysis parameters The optimal values of each factor of the pretreatment process responses were based on MultiObjective Numerical Optimization (Montgomery, 2001, Mathews, 2005). Reaction temperature (5060 oC), reaction time (48 h), and hydrogen peroxide concentration (13%) were tested as conditions for optimizing the saccharification process using RSM (Table 3). The second-order polynomial obtained was as follows: Reducing sugars (mg/g) = -586.403 + 15.319 X1 + 48.601X2 + 62.984X3 -0.110X1

2 -3.689X2 2

- 14.568X3 3 -0.043X1X2 -0.382X1X3 + 5.648X2X3 {R2 = 0.9511 (R2 adjusted = 0.9071)} 3 When the values from X1 to X3 were substituted in the above equations, the predicted responses were obtained (Table 3) Table 2 Experimental design matrix of the 23 CCD, observed and predicted values of reducing sugars after saccharification of treated raw biomass Run Temperature (oC) Time (min) % H2O2 Observed RSa Predicted RSa 1 76.8 6 2 165.95 156.66 2 50 4 3 91.85 99.50 3 60 6 3.6 164.1 154.56 4 60 9.4 2 160.13 171.15 5 60 6 2 163.5 169.38 6 60 6 2 165.69 169.38 7 70 8 3 184.2 188.20 8 60 6 0.3 94.85 101.78 9 50 4 1 85.23 83.07 10 50 8 1 123.69 114.05 11 50 8 3 181.25 175.65 12 70 4 1 106.86 114.30 13 43.2 6 2 113.16 119.85 14 70 4 3 103.97 115.46 15 60 6 2 165.92 169.38 16 70 8 1 147.67 141.87 17 60 2.6 2 97.56 83.93 18 60 6 2 176.01 169.38 19 60 6 2 174.35 169.38 20 60 6 2 170.34 169.38 aReducing sugars in mg glucose equivalent per g dry substrate The statistical significance of the model equation was evaluated by the F-test for analysis of variance (ANOVA), which showed that the regression was statistically significant. The Probability value for the regression(model) was 0.000, which indicated that the model was statistically significant using a confidence interval of 95%. The Model F-value (21.60) implied that the model was significant and there was only a 5% chance that a Model F-value could occur because of disturbance (error). The coefficient of determination ( R2) of the model was 0.9511, indicating again that the model was suitable in establishing relationships among the reaction variable. The R2 value explains that a 95% variability is attributed to the factors for the response. This also means only 5% of the total variation is not explained by the model. The adjusted determination coefficient is also high indicating a high significance of the model. The linear terms and quadratic terms, are highly significant (Table 3). The overall second-order polynomial equation for the enzymatic hydrolysis is as given in Equation 3. Two-dimensional contour plot and three-dimensional response surface curves were plotted to study the main and interactions between the various parameters during pretreatment of

the sugarcane bagasse and were used to determine the optimum levels of each factor required to obtain maximum response of the reducing sugars. Effects of individual factors on the reducing sugars yields are shown in Figure 1. Figure 1(a) shows the contour plot indicating that reducing sugars yields increased up to 175 mg/g dry substrate with increasing time and temperature. A maximum value is likely to be attained between 6075 oC and 89 h. Figure 1(c) of the surface plot also indicated that reducing sugars production increased between 150200 mg/g dry substrate for reaction time of 68.5 h and hydrogen peroxide concentration of 23%. Table 3. Analysis of variance (ANOVA) for regression model obtained from experimental design Source Mean square F-value P-value Regression 2444.23 21.6 0.000 Linear 911.38 8.05 0.005 Square 2224.76 19.66 0.000 Interaction 381.01 3.37 0.063 Residual error 113.15 Lack-of-Fit 200.36 7.72 0.021 Pure Error 25.94
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Reducing sugars %H2O2 Time (h)

(c) Figure 1. (a) Contour plot of Reducing sugars (mg/g) vs. Time and Temperature; (b) Surface plot of Reducing sugars (mg/g) vs. %H2O2 and Temperature; (c) Surface plot of Reducing sugars (mg/g) vs H2O2 and Time. The model equation for the response (reducing sugars yield) and the response surface and contour plots were utilized in determining the optimum process conditions. With all these

constraints in mind, the optimum cumulative response of 194.75 mg/g dry substrate (desirability of 1.00) was obtained at 63 oC, 8.5 h, and 3% H2O2 (Figure 2). Additional sets experiments at these specific conditions were performed to validate the optimized conditions. The validated reducing sugars yield at optimized pretreatment conditions was obtained to be 189.47 mg/g dry substrate. The experimental and predicted responses were found to be in close agreement, thus confirming the optimization process.
+ur ,ig h 1 -$ $ $$ .o/ 0 1 p tim a l d = 1-$ $ $ $ 2 a 3im um 4ed5uga y = 1 (& -" # * $ 1 -$ $ $ $ 0e s ir a b ility + om p o s i te $ -* 1 ) % * -' ) 1 ) % -' * ' & ( -* ' * ' & * -1 ) % 1 " ' -) 1 " ( 6 em p 6 im e 7,%1 % 8' % -) ) " ( 9 8) -& ) $ % 9 8% -( ' ) *9

Figure 2. Response optimization conditions of reducing sugars yield 4. CONCLUSIONS These investigations showed that hydrogen peroxide and sodium hydroxide are suitable to cause appreciable disruption to the lignocellulosic complex such that the treated material could be amenable to enzymatic hydrolysis. Pretreatments using a 23- central composite design of experiments showed temperature at 63 oC, reaction time of 8.5 h, and 3% H2O2 as validated optimized conditions. After third day of enzymatic hydrolysis of treated biomass with an enzyme loading of 25 filter paper units/g dry biomass, treated biomass loading of 2% and 50 oC incubation period, a maximum of 194.75 mg glucose equivalent/g dry substrate of reducing sugar was also recorded at the established pretreatment conditions. From the enzymatic hydrolysis, increasing the pretreatment conditions favoured the increased yield of the reducing sugars. REFERENCES Ayeni, A.O., Banerjee, S., Omoleye, J.A., Hymore, F.K., Giri, B.S., Deshmukh, S.C., Pandey, R.A., Mudliar, S.N. (2013). Optimization of pretreatment conditions using full factorial design and enzymatic convertibility of shea tree sawdust. Biomass and Bioenergy 48:130138. Ayeni, A.O., Hymore, F.K., Mudliar, S.N., Deskmukh, S.C., Satpute, D.B., Omoleye, J.A., Pandey, R.A.(2013). Hydrogen peroxide and lime based oxidative pretreatment of wood waste to enhance enzymatic hydrolysis for a biorefinery: Process parameters optimization using response surface methodology. Fuel 106:187194. Blasi, C.D., Signorelli, G., Russo, C.D., Rea, G. (1999). Product distribution from pyrolysis of wood and agricultural residues. Industrial Engineering Chemistry Research 138:22162224. Gould, J.M. (1984). Alkaline peroxide delignification of agricultural residues to enhance enzymatic saccharification. Biotechnology Bioengineering 24:4652. Gould, J.M. (1985). Studies on the mechanism of alkaline peroxide delignification of agricultural residues. Biotechnology Bioengineering 27:225231. Hsu, T.A. Pretreatment of biomass. In: Wyman CE, editor. Handbook on bioethanol: production and utilization. Washington: Taylor and Francis; 1996. p. 179212.

Iwo, G.A. and Hussaini,S.W.H. (2001). Variability of ploidy levels of three sugarcane species in Nigeria. Sugar Technology 3(4):166 170. Kim, S., Dale, B.E. (2004). Global potential bioethanol production from wasted crops and crop residues. Biomass and Bioenergy 26(4):36175. Li, S., Xu, S., Liu, S., Yang, C., Lu, Q. (2004). Fast pyrolysis of biomass in free-fall reactor for hydrogen-rich gas. Fuel Process Technology 85:12011211. Lin, L., Yan, R., Liu, Y., Jiang, W. (2010). In-depth investigation of enzymatic hydrolysis of biomass wastes based on three major components: cellulose, hemicelluloses, and lignin. Bioresource Technology 101:82178223. Lynd, L.R., Laser, M.S., Bransby, D., Dale, B.E., Davison, B., Hamilton, R., Himmel, M., Keller, M., McMillan, J.D., Sheehan, J., Wyman, C.E. (2008): How biotech can transform bio-fuels. Nature Biotechnology 26:169172. Ma, F., Yang, N., Xu, C., Yu, H., Wu, J., Zhang, X. (2010). Combination of biological pretreatment with mild acid pretreatment for enzymatic hydrolysis and ethanol production from water hyacinth. Bioresource Technology 101(24):96009604. Mathews, P. (2005). Design of experiments with MINITAB, Pearson Education Publications, New-Delhi. Metzger, J.O., Httermann, A. (2009). Sustainable global energy supply based on lignocellulosic biomass from afforestation of degraded areas. Naturwissenschaften 96:279288. Miller, G.L. (1959). Use of dinitrosalicylic acid reagent for determination of reducing sugar. Analytical Chemistry 31:426428. Montgomery, D.C. (2001). Design and analysis of experiments, Wiley Publications, New York. OSullivan, A.C. (1997). Cellulose: the structure slowly unravels 4(3):173207. Saha, B.C., Cotta, M.A. (2006). Ethanol production from alkaline peroxide pretreated enzymatically saccharified wheat straw. Biotechnology Progress 22:449453. Saha, B.C., Cotta, M.A. (2007). Enzymatic sacccharification and fermentation of alkaline peroxide pretreated rice hulls to ethanol. Enzyme Microbiology Technology 4:528532. Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., et al. Determination of structural carbohydrates and lignin in biomass: laboratory analytical procedure (LAP). Golden, CO: National Renewable Energy Laboratory; 2008 April. NREL Report No.: TP-510-42618. Contract No.: DEAC36- 99-G010337. Sponsored by the U.S. Department of Energy. Wheals, A.E., Basso, L.C., Alves, D.M.G., Amorim, H.V. (1999). Fuel ethanol after 25 years. Trends in Biotechnology 17:482487. Wyman, C.E. (2001). Twenty years of trials, tribulations, and research progress in bioethanol technology. Applied Biochemistry and Biotechnology 9193:521. Zhihong, Fu, Holtzapple, M.T. (2010). Fermentation of sugarcane bagasse and chicken manure to calcium caboxylates under thermophilic conditions. Applied Biochemistry and Biotechnology 162:561-578.

P-04 THE NIGERIAN CONTENT ACT AS A SPRING BOARD FOR INDUSTRIAL DEVELOPMENT Johnson T. Olajuyigbe Monitoring and Evaluation Directorate, Nigerian Content Development and Monitoring Board, Yenagoa, Bayelsa State. Johnson.Olajuyigbe@ncdmb.gov.ng ABSTRACT Nigeria though blessed with abundant human and natural resources still lags behind in terms of Industrial development and progress. Most of the Developmental Indices continued on downward trends as evidenced in poverty, unemployment, decaying infrastructures etc. With 50years of Oil and Gas exploration, production, exploitation and trillions of Naira accruing, basic infrastructures, and necessary amenities are still lacking. Out of $20billion annual Industry spend, less than $5billion is retained in-country as over 95% is taken out in terms of goods and services. One of the proffered solutions to these myriad of problems is the Nigerian Content Act (1), starting from the Oil and Gas Industry. It is worthy to note that most of todays industrialised nations developed on the back of this model thus providing a good benchmark. Within the three years of its implementation, the Nigerian Oil and Gas Industry Content Development (NOGICD) Act 2010 has yielded considerable results: employment generation, retention of in-country spend, capacity building, value addition amongst others. This Paper presents an overview of the Act, functions of Nigerian Content Development Monitoring Board (NCDMB) - the Federal Government Agency charged with the mandate of overseeing the implementation of the provisions of the Act, ongoing Initiatives and concludes that the Nigerian Content Act is indeed a spring board for the industrial development of Nigeria. A continued commitment to the Act will go a long way in actualising the Vision 20:20 (20:2020) Transformation Agenda of the Federal Government.

1.0 INTRODUCTION
Definition: Nigerian Content is defined as the quantum of value added to or created in the Nigerian Economy by a systematic development of capacity and capabilities through the deliberate utilization of Nigerian human, material resources and services in the Nigerian Oil and Gas Industry. Nigeria is the largest Oil producer in Africa and the 11 th largest in the world market, averaging 2.5million barrels per day and is currently the 5 th largest exporter of Crude Oil to the United States of America with Oil revenue making up over 90% of Nigerias foreign exchange earnings and 80% of total national income (2, 3).
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Despite this impressive profile, the contribution of the Nigerian Oil and Gas Industry to the National Gross Domestic Product (GDP) has been very minimal: 38.77% (current Basic Prices), 14.75% (1990 Basic Prices) (4). Out of the $20billion annual Industry spend, less than 5% is retained in-country. This has been a direct consequence of the noticeable absence of indigenous

participation in the Industry given that over 80% of the goods and services needed for Projects were imported into the country (5). Furthermore, in the greater part of the last four decades, the Nigerian Oil and Gas Industry has been dominated by major oil Companies with foreign contractors and expatriates workers employed to carry out Projects (Engineering, Procurement, Fabrication and Construction etc) in various onshore and offshore locations in the country. This has resulted in capital flight, paucity of jobs, little skills development, low capacity building and utilization of the indigenous workforce and in the long run a lack of sustainable economic development in Nigeria. The Federal Government introduced the Nigerian Content Act, aimed at championing the course for higher indigenous participation in the Sector and value addition for the nation. Under the Act, the utilization of Nigerian human and material resources for the provision of goods and services in the Industry within acceptable quality, health, safety and environmental standards are made mandatory in order to stimulate the development of indigenous capabilities ( 6, 7).

2.0NIGERIAN CONTENT ACT

The Nigerian Content Act known as Nigerian Oil and Gas Industry Content Development (NOGICD) Act 2010 was signed into Law on 22nd April 2010 by His Excellency, Dr. Goodluck Ebele Jonathan. This heralded a new implementation framework for the Nigerian Content Policy of Government. The main thrust of the Act is to maximize the utilization of Nigerian human resources, Nigerian-made goods and services. The Act provided the legal and Institutional framework for Nigerian Content development and established the Nigerian Content Development and Monitoring Board (NCDMB). 2.1 STRUCTURE OF THE NOGICD ACT 2010 The Act is divided into three (3) Parts of 107 Sections and a Schedule. Figure 1 gives the Structure of the Act. 2.2 KEY THRUSTS OF THE ACT The overarching concept of the Law is to have a single stand-alone Legislation that covers all activities pertaining to NC development in the Nigerian Oil and Gas Industry. Under the Law, the Board is the only Government Agency with the responsibility to develop, monitor and implement Programs to ensure steady growth of Nigerian Content. The key thrusts of the Act can be categorized into four (4) Segments:
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FIGURE 1: Structure of the NOGICD Act 2010

A. ORGANIZATION AND IMPLEMENTATION FRAMEWORK 1. Creates NCDMB empowered to enforce compliance, with elaborate structures including a professional Governing Council, Nigerian Content Consultative Forum (NCCF) and Nigerian Content Development Fund (NCDF). 2. Integrates NCDMB into the Planning and Contracting Process to ensure Nigerian Content COUNTS in all Industry operations and considerations. 3. Mandates utilization of electronic platform (NOGIC JQS) to cover Upstream, Midstream, Downstream, Independents etc. 4. Requires increased stakeholder engagements in the NCCF to create linkages to other Sectors including professional services. B. INDIGENOUS AND COMMUNITY PARTICIPATION 1. Requires increased participation by indigenes and defines indigenous Company. 2. Creates opportunity for integrating Oil Producing Communities into mainstreams Industry activities. 3. Mandates enlightenment and awareness Programs. C. DEVELOPMENT AND UTILIZATION OF LOCAL CAPACITY 1. Promotes Education, Employment, Training, Research and Development. 2. Requires multinationals to domicile portion of assets in Nigeria. 3. Promotes Indigenous Ownership of Equipment. 4. Mandates local capacity development - Gap analysis, design and implement interventions. D. NC TARGETS, COMPLIANCE MONITORING AND ENFORCEMENT 1. Sets steep targets for specific work items to be executed in Nigeria.
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2. Empowers Hon. Minister of Petroleum Resources to grant waiver under specific conditions. 3. Provides for performance monitoring, measurement and tracking compliance, 4. Stipulates penalty for non-compliance. 2.3 HIGHLIGHTS OF THE ACT Major highlights of the Act are that it: Provides legal backing for NC implementation. Gives first consideration to Nigerians in Employment and Training. Gives first consideration to Nigerian Independent Operators, exclusive consideration to Nigerian Indigenous Service Companies in all Projects, Contracts and Services. Gives first consideration to Services provided from within Nigeria and goods manufactured in Nigeria. Requires Operators to submit Nigerian Content Plan before carrying out any Project in Nigeria. Sets out specific targets for NC scope in all activities under Schedule of the ACT. Requires Operators to carry out Research & Development, Technology Transfer Programmes. Mandates Operators to utilize local Insurance, Legal and Financial Services. Requires Operators to submit different Statutory Reports quarterly, bi-annually and

annually. Requires 50% of Multi-national Companies Assets to be vested in Nigerian subsidiary. Defines Nigerian indigenous Company to be 51% owned by Nigerians. Mandates deduction of 1% from all Contracts for the establishment of NCDF. Stipulates Penalty for non-compliance. 3.0 NIGERIAN CONTENT DEVELOPMENT AND MONITORING BOARD (NCDMB) The Nigerian Content Development and Monitoring Board (NCDMB) is the Agency of the Federal Government vested with the mandate to make Procedures that will guide, monitor, coordinate and implement the provisions of the Nigerian Content Act 2010 and undertake an effective monitoring of the implementation. Figure 2 states the Vision, Mission and Medium Term Targets of the Board. KEY FUNCTIONS OF NCDMB Review, assess and approve Nigerian Content Plans developed by Operators. Participate in all contracting processes from Prequalification to Commercial. Award Certificate of authorisation for Projects that comply with Nigerian Content provisions.
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( 6 e ta in = ( ) bi ll ion out of = 2 ) bi ll ion a ve r a ge a nnua l Indu str y spe nd 0 2 Cr e a te ov e r + ) 9) ) ) dir e "t employme nt a nd tr a ining oppo r tun it ie s0 + E st ab lis h + to > ne/ Pipe M i lls to s e rv i"e Indust r y dema nds0 > D e v e lo p ( or 2 D o" ;y a rds a nd ma ? imi@e ut ili@a t ion o f e ?ist ing #h ip ya rds0 4 & ra n sforma t ion of o/ ne rsh ip profile of ma r ine a sse ts s uppor t ing Indust r y0 , Int e gr a t io n of ind ige ne s a n d busine sse s r es id ing in the Oi l produ" ing a re a s0 * Ca p tur e ove r 4 ) 1 * )3 o f a n ;ing se r vi" e s9 Insur a n"e r is; pla "eme nt s a nd .e g a l se r v i"e s

FIGURE 2: Vision, Mission and Medium Term targets of NCDMB

Figure 3 below shows NCDMB Organisational Structure.

FIGURE 3: NCDMB Organisational Structure

KEY FUNCTIONS OF NCDMB (CONTD) Set Guidelines and minimum content levels for Project related activities across the Oil and Gas value chain. Engage in targeted Capacity Building interventions that would deepen indigenous capabilities - Human Capital Development, Infrastructure and Facilities, Manufactured

Materials and Local Supplier Development. Grow and manage the Nigerian Content Development Fund (NCDF).
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Establish, maintain and operate the Joint Qualification System (NJQS) in conjunction with Industry Stakeholders and to operate the e-marketplace. Monitor Nigerian Content Compliance by Operators and Service Providers. This will be in terms of cumulative spending, employment created, sources of local goods, materials and services utilised on Projects and Operations. Conduct studies, researches, investigations, workshops and trainings aimed at advancing the development of Nigerian Content.

4.0 NCDMB INITIATIVES FOR INDUSTRIAL DEVELOPMENT

4.1 EQUIPMENT COMPONENTS MANUFACTURING INITIATIVE (ECMI) The Objective of ECMI is get Representatives of Original Equipment Manufacturers (OEMs) in Nigeria partner with the OEMs and establish facilities for manufacturing equipment components and parts in Nigeria. The Business Case for EMCI is based on the realization that local manufacturing of components used by Industry holds the key to creating jobs in the Industry, spend retention and industrialization of the economy. The Initiative operated in Phases ensures supplies of some vital equipment in the Oil and Gas Industry are allowed only after the Suppliers have committed themselves to credible Proposals on how they would domicile the manufacturing of some components within the shortest possible time. The Board then follows up to ensure that the OEM Representatives keep the commitments and begin manufacturing these components. NCDMB introduced Nigerian Content Equipment Certificate (NCEC), which makes equipment component or equipment spare parts manufacture a requirement in Tenders. Since the inception of the Initiative, over 500 certificates have been issued to Equipment Manufacturers and OEM Representatives who have met the technical requirements of NCDMB. This represents over $800million investment commitment within the next three years. 4.2 MARINE VESSEL OWNERSHIP STRATEGY (MAVOS) Activities in the Nigerian Oil and Gas Industry have over the years moved offshore with considerable amount channeled to Marine Services annually. A survey jointly conducted by NCDMB, NIMASA and other Industry Stakeholders in 2010 revealed the flight of over 90% of expenditure in the Maritime Sector of the Oil and Gas Industry to foreign economies where ownership of the various Assets were domiciled. MAVOS encourages construction of vessels in Nigerian Yards, promote ownership of marine vessels by Nigerians, stimulate flagging and registration of vessels in Nigerian and deepen Nigerian manning of marine vessels. Under the Scheme, Nigerian marine vessel owners and vessel built in Nigeria are pre-qualified to participate in Tenders based on a set of criteria established by the Board.
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A key component of the Scheme is the categorization of marine vessel Providers (Vendors) according to ownership status, where the vessel is built and manning structure. 4.3 OFFSHORE RIG ACQUISITION STRATEGY (ORAS) The Offshore Rig Acquisition Strategy (ORAS) and Marine Vessel Ownership Strategy (MAVOS) mandate the use of only rigs or vessels with genuine Nigerian part ownership or equity. The key elements of ORAS are: using a Nigerian operating Company for contracting, phased increase in rig ownership by indigenous Company (to meet the Act requirement of 50%),

structured and long term financing plan for rig owners, supports pool of indigenous Companies partnering with foreign Company to own offshore rig. The impact in the last three years has been encouraging as Nigerians now own land, swamp, jack up and rigs while also taking equity proportion of deep offshore rigs. Major challenges include high capital outlay required for acquiring rigs, low indigenous competence in operating rigs as specialized knowledge is required. 4.4 PIPEMILL SCHEME Steel pipes are critical inputs in the Oil and Gas Industry in terms of utilization; essential for transporting hydrocarbons. Steel pipes therefore has high potential for employment generation, local value addition and retention of Industry spend. The projected annual Industry demand of line pipe is over 800,000tons, arising from the demands from Gas Master Plan, replacement of aged pipes and new fields development Projects against the current supply opportunity of 100,000 MT (HSAW) per annum. This is an opportunity for Investors. NCDMB is promoting the establishment of Pipe mills in Nigeria. The initiative involves a pilot scheme where the Board is directly involved in Project development activities (land acquisition and market intelligence). In this regard, land has already been acquired in Polaku (Bayelsa State) to support the establishment of a 250 MT Pipe mill. 4.5 HUMAN CAPITAL DEVELOPMENT Sections 28, 29 and 30 of the NOGICD Act 2010 charge the Board with the responsibility to create employment, develop training facilities and coordinate training on the back of Oil and Gas Projects. This was further highlighted when studies carried out pre-enactment of the Act revealed considerable skill gap in specialized services in the Industry, despite the impressive numbers of graduates and technicians in Engineering and Oil and Gas related disciplines produced by Nigerian Schools. In a bid to address the challenges, the Board introduced several human capital development programmes in collaboration with operating Companies; Service Companies, Petroleum Technology Development Fund (PTDF) and other Stakeholders to train engineers, technicians, welders and other Industry hands. Over 30,000 training and employment opportunities have been created in the last three years of the Acts implementation. The Board is also sponsoring specific training to meet immediate Industry and local community needs. In this
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regard, the Board will train 1,000 Nigerians on Environmental Remediation and 50 others on a pilot scheme for Geosciences. In order to achieve her goal in human capital development, NCDMB has adopted a two-pronged approach: DIRECT INTERVENTION Identify specific areas with skill shortages and provide training opportunities INDUSTRY REGULATORY INTERVENTION Through regulations, NCDMB aims to raise the skill levels of Nigerians. This is by using 10% of man-hours of every Project for training, giving first consideration to Nigerians. The Board is providing institutional support to Oil and Gas Trainers Association of Nigeria and Petrofac (an international Training Institute) towards the establishment of Training Centres of Excellence (TCEs). The TCEs will provide internationally certified training and certification opportunities for over 10,000 Nigerians over the medium term in areas of Field Exploration, construction of Oil and Gas production facilities and other related skills. 4.6 NIGERIAN CONTENT EMPLOYMENT INITIATIVE (NCEmI) The Nigerian Content Employment Initiative (NCEmI) is the NCDMB model for creating

employment opportunities for Nigerians on the back of Oil and Gas Projects. It is the procedure for structured interface between key stakeholder groups such as Training Center of Excellence, Service Companies, Operators and NOGIC JQS data base in the employment and training value chain. NCEmI is built on four key pillars: Certification of Service Companies requires all Service Companies operating in the Oil and Gas Industry to submit a pupilage Program describing how they will create employment opportunities for Nigerians within their Organisation. Candidate selection through JQS All candidates that will be nominated for the NCEmI will be selected from the JQS. Selection of Training Centers of Excellence TCEs will be established to meet the demand side of the NCEmI. Employment Management This is concerned with the placement of trainees and ensuring that individuals who are trained receive permanent employment letters from Service Companies that successfully win Contracts. Individuals whose provisional employments are not immediately converted into permanent employment will have their profile in the JQS until new opportunities are available.
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4.7 NIGERIAN CONTENT JOINT QUALIFICATION SYSTEM (NOGIC JQS) The NOGIC JQS electronic platform (http://portal.nogicjqs.com) is anchored on Sections 55 and 56 of the Nigerian Content Act. It is the sole system for NC registration and prequalification of Contractors in the Industry. The platform is used to consolidate data of Stakeholders activities and constitute a databank of available capacities. The Board also uses the platform for: Verification of Contractors capacities and capabilities Evaluation of application of NC in the operations of Oil Companies and Contractors. Serves as a database pool for national skills development. NOGIC JQS, which is distinct from NIPEX JQS went on live on 16th August 2011and has been successfully used in the application process for the Oil Spill Management and Environmental Remediation Training Program. The Portal is divided into three broad Sections namely: Individual Module, Service Companies and Operator Module. NOGIC JQS has been successfully used in the following Areas: Individual Competency 14,226 Individual records and their accompanying documents Service Companies currently 728 active Service Companies Operators currently 6 major, and 9 marginal field Operators Approved Expatriate Quota uploaded 24 Expatriate Quotas Waivers uploaded 5 Wavers NCEC Management presently 189 Certificates are uploaded. 4.8 NIGERIAN CONTENT DEVELOPMENT FUND (NCDF) The NCDF was set up by the Board in line with provisions of the Act (Section 104) to cater for capacity building activities as well as fund the development of critical facilities needed in the Industry. The utilization of the Fund is split into two components:

 Partial Guarantee (70%) to meet working capital needs of the local supply chain. The benefits are: 50% interest rebate for Borrowers, longer tenure of two to five years, available for Asset acquisition. Capacity Development Component (30%) for direct capacity development by the Board such as Infrastructural development, facility upgrade, training, attachment, sponsorship, workshop, development of Industry Data Center. An Advisory Committee comprising IOCs, Bank of Industry (BOI), Petroleum Technology Association of Nigeria (PETAN) and Oil and Gas Trainers Association of Nigeria (OGTAN) advises the Board on the application of the Fund while a Fund Manager has been appointed to manage it. This will give the Industry comfort regarding the transparency of managing the Fund.
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4.9 EXPATRIATE QUOTA MANAGEMENT (EQM) Section 33 of the NOGICD Act 2010 reposed the responsibility of Expatriate Quota Management on the Board. This is to regulate the use of foreigners for jobs. It is also a platform that enables Government identify skill gaps within the Industry. As part of the second phase of implementation of EQM, expatriates working in the Industry are now required to undertake Biometric Registration. The exercise will capture details of all foreigners working for operating and services Companies on the NOGIC JQS. This will assist the Board to electronically track the numbers of expatriates in the industry, their length of stay, skill set compliance with provided succession plans and expected date of exit. 4.10 NIGERIAN OIL AND GAS INDUSTRIAL PARK STRATEGY (NOGIPS) The goal of NOGIPS is to facilitate new business start-ups, enterprise incubation and technology acquisition. This is by supporting the growth of Small and Medium Enterprises through mentoring by international Original Equipment Manufacturers (OEMS) and other multinationals. NOGIPS will create enabling environment for productive employment of skilled and semiskilled workforce, enhance competitiveness of locally made goods and increase utilization in the Oil and Gas Industry. Presently, the scope of the scheme covers the nine Oil producing States: Abia, Akwa Ibom, Bayelsa, Cross River, Delta, Edo, Imo, Ondo and Rivers. The Frame work for the implementation of NOGIPS is anchored on the following Principles: Small and medium Enterprises in Nigeria account for 75% of employment, contribute 10% to GDP and 3% to export. Majority of entrepreneurs in the Oil communities are SMEs, therefore NOGIPS will focus on developing the local SMEs. The local SMEs will partner with international manufacturers or OEMs to establish manufacturing facilities within the Park. State Governments may provide land and support development of basic infrastructure: roads, electricity, communications, water, gas etc. In line with Section 47 of the Act mandating Operating Companies to establish facilities in Nigeria, such Companies are expected to support the Park through contributions to infrastructural development, support businesses in the Park with work. 4.11 CREATING LEGACIES FROM MAJOR INDUSTRY PROJECTS Nigeria in the 50 years of Oil and gas operations built four giant Refineries, Petrochemical Plants, LNG Trains, FPSOs and laid over 5,000kms of Pipelines. None of these Projects left legacies or inspired major repair facilities to service the Projects after completion. These were grave mistake which ultimately threw up several operational challenges for the Projects, the Industry and the Policy. Using the instrumentality of the Act, the Board now seeks to ensure that every major Oil and Gas

Project leaves at least one legacy which is critical to the long term needs of the Industry and employ Nigerians after the Project. Already the Board has worked with Operators and other
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Industry Stakeholders to agree on key legacies that major Projects such as Egina, Bonga, Erha, Brass LNG, NLNG 7+ would leave behind and has taken steps to make them a reality.

5.0 CONCLUSION
The Nigerian Oil and Gas Industry Content Development (NOGICD) Act 2010, a major aspect of the Transformation Agenda of the Federal Government, will bring the much desired industrialisation of Nigeria. This is driven by the huge expenditures and mega Projects in the Oil and Gas Industry. The Act is set to achieve sustainable development of the nations economy through the stimulation of industrial development, growth of local capacities, building of a skilled national work force and the creation of a competitive supplier base. The various Initiatives embarked upon by the Board are yielding laudable results. There are investments in new facilities and upgrading existing ones, new jobs created, people trained, jobs designated for the Nigerian market, increased in-country spend. Today, 90% of Engineering Design is being done in Nigeria, about 50% of Fabrication in our Yards and focus is also on increasing Manufacturing. Following recent developments in the Oil and Gas Industry as enumerated above, it is obvious that the Nigerian Content Act is a veritable tool for the industrial development of Nigeria.

REFERENCES
(1) Nigerian Oil and Gas Industry Content Development Act 2010, National Assembly, Abuja, April 2010. (2) Nigeria Revenue Watch Institute, www.revenuewatch.org. (3) Festus E and Gowon D (2004), Law and Petroleum Industry in Nigeria, Current Challenges, Pipeline and Gas Journal, July 1st, 2007. (4) Federal Republic of Nigeria (The Presidency), 2012 and Estimate for Q1, 2013 GDP for Nigeria, National Bureau of Statistics, CBD, Abuja (www.nigerian stat.gov.ng). (5) Maeba Lee Ledogo (2010), The Nigerian Oil and Gas Industry Content Development Act: Simplified, Yaliam Press Ltd. (6) Serena-Dokubo Spiff David (2011), Understanding the Nigerian Oil and Gas Content Development Act 2010, NCDMB Sensitisation Programme for Bayelsa State. (7) Olisa Francis (2011), The Nigerian Content Development Act: Critical Analysis and Overview, NCDMB Sensitisation Programme for Imo State. (8) Chizea Chinelo Amake (2010), The Nigerian Content Development Act: Issues and Challenges (Marine and Logistics Perspectives), Nigerian Content Consultative Forum. (9) Onyeka Samuel (2010), The Nigerian Content Act: Building Capacities and enhancing Opportunities in the Insurance Sector, Nigerian Content Consultative Forum. (10) Usoro Mfon (2010), Nigerian Content Act: Perspective on Legal Profession, Nigerian Content Consultative Forum.

P-05 Predi"tive Modeling and Dete"tion of Oil Pipeline .ea;age

'0C O6G'9 E0E E!!IONG9 E0 'A<EN59 Dept0 of Chemi"al Engineering9 !ederal 5niversity of &e"hnology9 O/erri 'bstra"t 1il leaDage has been part of oil industry operational problems- <t normally occurs as a result of cracD in the pipeline due to fatigueEcorrosion, and nonFdetection of it early enough, has compounded the problem, leading to progression into e3plosionE spills and occasionally fire!, /ith the attendant huge costs and destruction6hus in this paper, the authors haGe deGeloped simple but efficient model for early predictionEdetection of oil leaDage>ll that is needed as inputs to the model areH the pipeline inlet (departure) and outlet (arriGal) flo/rates and pressures, as /ell as an accurate estimate of the pipeline system friction factor- Iith these, the oil leaDage Juantity, the location in the pipeline /here it occurs (leaDage point), and the e3tent of pipe damage (leaDage area), can be determined by using the model- 6his /ill ensure early and prompt remedial action that /ill minimiKe losses and damage occasioned by oil

leaDs6o ensure high sensitiGity, accuracy, reliability and robustness of the model prediction, smaller units liDe pascal should be used to replace the current oil field units, liDe, psi, or simply incorporated as an adLunctBey/ordsH 1il, pipeline, leaDage, spill, e3plosion, modeling, prediction, detection(0 Introdu"tion Bsually normal leaDage inGolGes cracD, due to corrosion, strain, etc, in the pipeline /hich increases /ith time due to fatigue, o3idation, and pressure of the fluid- <f unnoticed in time, the cracD progresses until a critical point /hen it /ill rupture and e3plode, thus result in spill, /here large Golumes are discharged into the enGironment,itherto oil pipeline leaDage detection inGolGes e3ternal (direct) and internal (inferential)- :3ternal based methods detect leaDage outside the pipeline and include traditional procedures such as rightFofF /ay inspection by line patrols, as /ell as technologies liDe hydrocarbonEacoustic sensing Gia fibre optic or dielectric cables- <nternally based methods, also Dno/n as computational pipeline monitoring, use instruments to monitor internal pipeline parameters(i-e-, pressure, flo/, temperature, etc), /hich are inputs for inferring a product release by manual or electronic computation(API,1995a) - 6he method of leaD detection selected for a pipeline is dependent on a Gariety of factors including pipeline characteristics, product characteristics, instrumentation and communication capabilities, and economics- ?ipeline systems Gary /idely in their physical characteristics and operational functions, and no one e3ternal or internal method is uniGersally applicable or possesses all the features and functionality reJuired for perfect leaD detection performance- ,o/eGer the chosen system should include as many of the desirable leaD detection utilities as possible6he history of oil industry haGe been dotted /ith incidences of oil spills ( NOAA, 1992; The Mariner Group, 2008)- @acD home here in ;igeria, the story is the same, including the recent ones discoGered in :Ligbo , .agos by a .andlord /ho found traces of oil in his /ell( http://allafrica.com/stories/201308261063.html ), and the M6A patrol team discoGered oil leaDs close to a signpost marDer N?F'" located around ?uloDiriE2oney =round ,bet/een >damaDiri and +reeD ' general area(Nigerian Ne/s 2)(+ )6hus these leaD detection methods generally inGolGe physical inspections, ,inGestigations and analysis of collected field data, /hich Ludging from the usual terrain of the pipeline systems , and sensitiGity of the oil field standard instrumentations, results in delays /hich inGariably results in late detection and more damage liDe spills and enGironmental pollution, /ith its attendant high costs6herefore this /orD inGolGes deGeloping models /hich can predictEdetect early leaDs, and the location of the long

distant pipeline /here it occurs and the Golume and area of leaDage point including progression to rupture and e3plosion, so that remedial action can be properly channeled before greater harm results-

2. Model Development 2.1 Theoretical Principle

+onsider an oil pipeline segment sho/n in the figure belo/H 0eparture(inlet) pressure H?in >rriGal (outlet) pressure ,?_out 0eparture(inlet) flo/rate,Oin >rriGal(outlet) flo/rate,Oout . Ai g-1H 1il pipeline segment <t is generally Dno/n that ?in P ?out, as a result of pressure drop, Q?. due to frictional resistance as the fluid flo/s along the pipelength, .- 6hus ___ _ ___ _ _ _- (1) ___has been correlated in terms of fluid properties to be generally giGen asH ___ _ 1E%___R_E _- (%) /here the friction factor f is a function of 4eynolds number 4e = dCSET- Aor instance at .aminar flo/ regime(4e U= %1$$), f = '&E4e, /hile for turbulent flo/(4e P %1$$), empirical correlations and charts are aGailable( ) 0eparture(inlet) pressure H?in >rriGal (outlet) pressure ,?_out

:Q_out
0eparture(inlet) flo/rate,Oin 1 % >rriGal(outlet) flo/rate,Oout .F . Aig-% H @roDen oil pipeline segment 5uppose /e breaD the pipe into t/o segments,1 and %, /ith lengths , and .F , as sho/n in the fig-% /ithout leaDage through the GalGe, thenH ___ _ 1E%___R_E _ (*) ___ _ 1E %___R__ _ __E_ (&) 6hus the total pressure drop for the /hole length becomesH ___ _ ___ _ 1E%___R_E_ _ 1E%___R__ _ __E _ _ 1E%___R_E_ _ __ _ (#) thus frictional pressure drop for a pipeline system is additiGe>ssuming that leaDage no/ occurred through the GalGe at the pipe length, , then, under normal conditions, the e3it

flo/rate or flo/rate do/nstream of the leaDage point, (i-e- bet/een length .F ) /ill no/ be lo/er than the inlet or upstream flo/rate before the leaDage(i-e- length )- 5ince f and G are related to the flo/rate, the frictional pressure drop in this case, ___, becomesH ___ _ 1E% __ _ ___R _E _ + 1E% __ _ __R(_ V _)E _ = 1E% __ _ ___R _E _W_E_ + __ _ __R E __ _ ___R(1 V _E_)X 6hereforeH ___ = ___W_E_ + __ _ ___R E__ _ __R(1 V _E_)X (') <n the case of laminar flo/H __ = '&EYZ_ = '&E( ___ _E[) __ = '&EYZ_ = '&E( ___ _E[) 7\] __ = (__E) ; __ = (_E), thus substituting into the eq.6 and

simplifying: ___ = = ___W_E_ + ( _ E (__(1 V _E_)X (7) By defining R as the ratio of the quantity leaked, (+,F- to the inlet flowrate (__, thus: Y = (+,F-E (__ Thus (+,F- = (__Y But (+,F- = (__ ^ ( _ Thus Y = ((__ ^ ( _ )E ($1 And ( _ = (__(1 V Y) Substituting into eq.7. ___ = ___W_E_ + (1 V Y)(1 V _E_)X (8) From the above eq it follows that, upstream pressure drop, <P1 is: ___ = ___W_E_X And downstream pressure drop, , <P2 is: ___ = ___ (1 V Y)(1 V _E_) Thus ___ = ___ + ___ = ___W_E_X + ___(1 V Y)(1 V _E_) ___E___ = 1 V (1 V _E_)Y (9) Since X/L and R are less than 1, it means that the RHS is less than 1 and by extension the LHS, <PX/<PL, thus the outlet pressure when there is leakage, Pin - <PX, will be higher than when there is no leakage, Pin - <PL . We know this is not the usual case, as the outlet pressure will be lower when there is leakage, i.e. <PX/<PL,>1, thus we need to include a correction term: the pressure drop due to leakage, <P3. 2.2 Methodology The framework adopted is to link the pressure drop due to leakage, <P3 to the outlet/discharge pressure drop due to friction, <P2, using the same analogy as linking the pipe fittings(valves, elbows, tees) pressure drop in terms of equivalent length of straight pipe friction pressure drop( Perry & Green, 1999; Rice, R.G; 1995). Thus recall that <P =1/ 2 f = v (L )/ d and for laminar flow, reduces to: <P =128TQL/d4 => <P.A2/Q = 128TL(16/>2) = constant, K Therefore <P2.A2 2/Q2 = <P3.A3 2/Q3 <P3/<P2 = (A2

2/Q2 )

/ (A3 2/Q3 )= A2 2Q3 / A3 2Q2 (10) By defining AR (or AR) = A3/A2, and making the substitutions: Q3 = Qleak = Qin.R; Q2 = Qout = Qin(1R), into eq .10, we have <P3 = <P2.R/{(1-R).AR 2} (11) Thus the total pressure drop following leakage becomes, by combining eqs:9 and 10 <PX= <P1 +<P2 +<P3 = <PL{X/L} + <PL (1-R)(1-X/L) +<P2 . R/{(1-R).Ar 2} thus ___E ___ = 1 + (1 V _E_)(Y) % _ *&# V 1' (11) Thus only the ratios X/L and AR are the two unknowns to be determined. To test the consistency of the equation, let us perform simulation and dimensional analysis using the equation, as shown below: 2.3 Simulation and Dimensional Analysis Table 1 shows properties/process parameters for a typical oil pipeline system: Table 1: TYPICAL OIL PROPERTIES
Inlet Pressure9 Pin C *$$$ psi = *$$$ 3 '-)(&"' =%$')&-%)$ N?a = %$')&%)$ ?a Pipeline length9 . C #$ N2 = #$$$$ m Inlet flo/rate9 Din C )$$$ bblEhr=%1#'$ in*Es = %1#'$ 3 (1E1%)* 3 $-$%)*1" m*Es =$-*#** m*Es 8is"osity9 E C # ft%Es 3 #' lbEft* = %)$ lbEft-s = %)$ 3 $-&#*#(% Dg E $-*$&)m -s= &1'-')' Dg Em-s Density9 F C #' lbEft* = $-$*$" lbEin* = #' 3 $-&#*#(% DgE$-$%)*1"m* =)('-((" DgEm* Internal diameter9 d C 1( in = 1( in 3 %#-& mmEin 3 1E1$$$ mEmm =$-&)%' m

Thus by varying the fail ratio R along the different segments/fail length, X of the pipeline, and using eqs 2 and 1, the total pressure drop, <PX, will be found from where the exit pressure, Pout = Pin - <PX ,in each case, can be found, using the values in table 1 and tabulated in table 2 below: Table 2 : Simulation results of exit(arrival) pressure for varying X and R for A R = 0.5
R= 0 R= 0.1 R= 0.2 R= 0.3 R= 0.4 R= 0.5 R= 0.6 R= 0.7 R= 0.8 R= 0.9 X=5000 15157672 .7 13665488. 68 12173304. 7 10681120. 72 9188936.7 35 769675 3

6204568 .8 471238 5 322020 1 172801 7 10000 15157672 .7 13831286. 9 12504901. 14 11178515. 38 9852129.6 16 852574 4 7199358 .1 587297 2 454658 7 322020 1 15000 15157672 .7 13997085. 12 12836497. 58 11675910. 04 10515322. 5 935473 5 8194147 .4 703356 0 587297 2 471238 5 30000 15157672 .7 14494479. 78 13831286. 9 13168094. 02

12504901. 14 118417 08 1117851 5 105153 22 985213 0 918893 7 25000 15157672 .7 14328681. 56 13499690. 46 12670699. 36 11841708. 26 110127 17 1018372 6 935473 5 852574 4 769675 3 30000 15157672 .7 14494479. 78 13831286. 9 13168094. 02 12504901. 14 118417 08 1117851 5 105153 22 985213 0 918893 7 35000 15157672 .7 14660278 14162883. 34

13665488. 68 13168094. 02 126706 99 1217330 5 116759 10 111785 15 106811 21 40000 15157672 .7 14826076. 22 14494479. 78 14162883. 34 13831286. 9 134996 90 1316809 4 128364 98 125049 01 121733 05 45000 15157672 .7 14991874. 44 14826076. 22 14660278 14494479. 78 143286 82 1416288 3 139970 85 138312 87 136654 89

> graphical preGie/(fig-1 ) of table % sho/s they are all straight line graphs /ith positiGe slopes- 6hus based on Y= a + b , Y=arriGal pressure, =Aail length, the coefficients, a and b are eGaluated for each 4 and sho/n in table * and

represented in figsH %(a \b) 6able *H +oefficients a and b Gs 4 4 = 4= $ 4= $-1 4= $-% 4= $-* 4= $-& 4= $-# 4= $-' 4= $-" 4= $-) 4= $-( a 1#1#"'" %-" 1*&(('($ -&' 11)&1"$) -%' 1$1)*"%' -$' )#%#"&*)#& ')'"" '% #%$("" (-# *##1" (" 1)(*) 1# %*#)* %-) b $ **-1#('& &$* ''-*1(%) )$" ((-&")(* %1 1*%-'*)# "'1 1'#-"( )% 1()-(#" )' %*%-11 "# %'#-%" "% %()-&* ')
1$$$$$$$ 11$$$$$$ 1%$$$$$$ 1*$$$$$$ 1&$$$$$$ 1#$$$$$$ 1'$$$$$$ $ 1$$$$ %$$$$ *$$$$ &$$$$ #$$$$
'rrival$E?it%pressure 9 Pa

Pipe fail length9G9 m !ig0(7 'rrival$E?it% preesure vs0 pipe fail length for different lea;age ratios 4= $

4= $-1 4= $-% 4= $-* 4= $-& 4= $-# 4= $-' 4= $-" 4= $-) 4= $-( $ %$$$$$$ &$$$$$$ '$$$$$$ )$$$$$$ 1$$$$$$$ 1%$$$$$$ 1&$$$$$$ 1'$$$$$$ $ $-% $-& $-' $-) 1 "oeft9 a 6 fig02a7 "oeft9 a vs 6 coeff, a Gs 4

showing that both coefficients exhibit 1stOrder Linear relationships with the failure ratio, R . thus: " = 1-#1#"'"H + $" V 1-'#"()%H + $"Y, 7 = %-1#')&)H V $' + **1-#('&Y substituting into eq.. _ = 1-#1#"'"H + $" + V1-'#"()%H + $"Y + (%-1#')&)H V $' + **1-#('&Y)_ Or _ = 1-#1#"'"H + $" V **1-#('&(#$$$$ V _)Y (12)
Bsing eJ aboGe, the resulting table is sho/n belo/H 6able &H 2odel Galues for table % 4= $ 4= $-1 4= $-% 4= $-* 4= $-& 4= $-# 4= $-' 4= $-" 4= $-) 4= $-( #$$$ 1#1#"' "* 1*''#&)( 1%1"**$# 1$')11%1 (1))(*" "'('"# * '%$&#' ( &"1%*) # *%%$%$ 1 1"%)$1 " 1$$$$ 1#1#"' "* 1*)*1%)" -* 1%#$&($1 -' 111")#1# -( ()#%1*$%

)#%#"& # "1((*# )-) #)"%(" * &#&'#) " *%%$%$ % 1#$$$ 1#1#"' "* 1*(("$)# -# 1%)*'&() 11'"#(1$ -# 1$#1#*%* (*#&"* ' )1(&1& ) "$**#' 1 #)"%(" * &"1%*) ' %$$$$ 1#1#"' "* 1&1'%))* -" 1*1')$(& -& 1%1"**$# -1 111")#1# -) 1$1)*" %" (1))(* "-% )1(&1& ) "1((*# ( '%$&#' ( %#$$$ 1#1#"' "* 1&*%)')1 -( 1*&(('($ -)

1%'"$'(( -" 11)&1"$) -' 11$1%" 1) 1$1)*" %' (*#&"* # )#%#"& & "'('"# * *$$$$ 1#1#"' "* 1&&(&&)$ -1# 1*)*1%)" -* 1*1')$(& -&# 1%#$&($1 -' 11)&1" $( 111")# 1' 1$#1#* %* ()#%1* $ (1))(* " *#$$$ 1#1#"' "* 1&''$%") -*# 1&1'%))* -'( 1*''#&)( -$& 1*1')$(& -*( 1%'"$" $$ 1%1"** $# 11'"#( 1$ 111")# 1'

1$')11 %1 &$$$$ 1#1#"' "* 1&)%'$"' -#' 1&&(&&)$ -1* 1&1'%))* -'( 1*)*1%)" -%' 1*&((' (1 1*1')$ (& 1%)*'& () 1%#$&( $% 1%1"** $# &#$$$ 1#1#"' "* 1&((1)"& -") 1&)%'$"' -#' 1&''$%") -*# 1&&(&&)$ -1* 1&*%)' )% 1&1'%) )& 1*(("$ )# 1*)*1% )" 1*''#& )( >n >;1C> test bet/een Galues in tables % and & sho/ed no significant Gariation, sho/ing that the models are best fit to the data- thus the general e3pression becomesH _ = ) V `(> V _)Y (1*)
$ %$ &$ '$ )$ 1$$ $ $-% $-& $-' $-) 1

"oeft9b 6 fig02b7 "oeft9b vs06 coefft,b Gs-4

20+0( Effe"t of '6 variation on the "oeffi"ients '9 9 C ;ote that the aboGe simulations that gaGe the aboGe Galues of >, @, and + are based on >4=$-#- @y no/ Garying the >4, gaGe the follo/ing results sho/n in table- @elo/H 6able #H Galues of coefficient >, @, + for Garying >4 >@+ >r = $-%# 1#1#"'"& 1'#"-()%* #$$$$ $-*"# 1#1#"'"* '"#-&"&%&*% #$$$$ $-# 1#1#"'"* **1-#('&''1 &((((-(('$( $-'%# 1#1#"'"* 1"%-&*$1&#* #$$$$-$$*(1 $-"# 1#1#"'"* )#-('(&#(#* &((((-(('$( 6hus only coefft, @ Garies /ith >4, and the appropriate relationship is found by regression analysis to beH @ = F%%1-$'&* + 11$-#*%% (1+ 1E>4 %) >nd Gerified as sho/n in fig-* belo/H

thus by substituting this value of B into eq and rearranging: _ = ) ^ 11$-#*%%@ > ^ _ +(Y) % _ *&# V 1' (14) Thus the general expression becomes: _ = ) ^ `@ > ^ _ +(Y)% _ *&# V 1' (15)
6o linD these coefficients, >, @ and + to the process parameters ,and hence deriGe the generaliKed e3pression let]s see the effects of the process parameters on these coefficients- 6hus by Garying the process parameters and repeating the simulations, the results are sho/n in table '6able 1H Gariations ofd coefficients >, @, + /rt process parameters ?rocess parameters > @ + Giscosity &1'-')' 1#1#"'"* **1-#('&''1 &((((-(('$( &1'-")' 1#1#'*&' **1-'"'$%#& #$$$$ &1'-))' 1#1##$%$ **1-"##'1#% &((((-(('$(
$ #$$ 1$$$ 1#$$ %$$$ $ $-% $-& $-' $-) Coeft0 'r !ig0+7 Model vs0 E?pt values for "oeft0 @(model) @(data)

density )('-((" 1#1#"'"* **1-#('&''1 &((((-(('$( )("-$(" 1#1#"'"* **1-#('&''1 &((((-(('$( )("-1(" 1#1#"'"* **1-#('&''1 &((((-(('$( Alo/rate

$-*#** 1#1#"'"* **1-#('&''1 &((((-(('$( $-&#** 1*#(**(1 &%#-&#**'(1 #$$$$ $-##** 1%$%(1$( #1(-*1$%&1" #$$$$ ?ipe .ength #$$$$ 1#1#"'"* **1-#('&''1 &((((-(('$( #$$$1 1#1#"#'% **1-#('&*## #$$$1 #$$$% 1#1#"&#% **1-#('&*## #$$$% 0eparture(<nlet) ?ressure %$')&%)$ 1#1#"'"* **1-#('&''1 &((((-(('$( %$')&%)1 1#1#"'"& **1-#('&''1 &((((-(('$( %$')&%)% 1#1#"'"# **1-#('&''1 &((((-(('$( diameter $-&)%' 1#1#"'"* **1-#('&''1 &((((-(('$( $-#)%' 1)$)%1') 1#'-1%'"%&% &((((-(('$( $-')%' 1(*$*&&% )%-)#$%)$"' #$$$$-$$*(1

Thus A=f(viscosity , Flowrate , Pipe Length ,Departure(Inlet) Pressure ,diameter ) B=f(viscosity ,Flowrate , diameter ) C=f( Pipe Length ) Rearranging symbolically as follows: f(A, T, q, L, Pin ,d) = 0 f(B ,T, q, d) = 0 f(C, L) = 0 Thus by inspection/dimensional analyses their functional relationships are derived as follows: First these functional relations can be arranged in the form of a Dimensional Matrix where we have the variables written on the top and their corresponding dimensions in a vertical column underneath as shown below for the case of A coefficient: A T q l dp d M111010 L -1 -1 0 1 -1 1 T -2 -1 -1 0 -2 0 The rank,r, of a matrix is defined to be the size of the largest square submatrix that has a non-zero determinant(MDTERM). Thus forming and testing the submatrix, for instance: A T q A q dp T q l T dp d M111M111M110M110 L -1 -1 0 L -1 0 -1 L -1 0 1 L -1 -1 1 T -2 -1 -1 T -2 -1 -2 T -1 -1 0 T -1 -2 0 MDTERM = -1 MDTERM =0 MDTERM = 0 MDTERM = 1 Since there exist at least one non-zero 3rd order determinant, the rank of the matrix, r = 3. Note that has this failed, we would have gone to test 2nd order determinant /matrix.

At this juncture, Buckingham pi-theorem (www.potto.org/FM/fluidMechanics.pdf) can be used to determine the functional relationships existing between the variables as follows: Let q I , q2 . . . . qn be n variables involved in a particular problem, so that there must exist a functional relationship of the form F(q l, q2, ---qn) = 0. Buckinghams theorcm states that the n variables can always be combined to form exactly (n-r) independent nondimensional variables >i, where r is the rank of the dimensional matrix. Thus the functional relationship reduces to the form F(>1, >2, --- > n-r) = 0 Each > number is called a nondimensional parameter and the method of forming them is based on underlying principle of dimensional homogeneity, which states that all terms in an equation must have the same dimension.thus they are formed by a product of the variables, qi(expressed in terms of fundamental units) raised to some powers determined by the application of the underlying principle of dimensional homogeneity. This will be illuatrated as follows: We first select any 3(= r) of the variables as the "repeating variables", which we want to be repeated in all of our nondimensional parameters. These repeating variables must have different dimensions, and among them must contain all the fundamental dimensions M, L, and T. In many fluid flow problems, we choose a characteristic velocity(or flowrate), a characteristic length(or diameter), and a fluid property(density) as the repeating variables. Thus for the pipe flow problem, let us choose q,d and = as the repeating variables. Although other choices would result in different set f nondimensional products, we can always obtain other complete sets by combining the ones we have. Therefore, any choice of the repeating variables is satisfactory. Each nondimensional product is formed by combining the three repeating variables. For example, let the first dimensional product be taken as: f(A,T,,q,l,dp,d) = 0 >1 = (T)a (d)b ( Q)c .A Others are also formed as follow s: >2 = (T)a (d)b ( Q)c .L >3 = (T)a (d)b ( Q)c .dp The exponents a,b, and c are obtained from the requirement that >1 , >2, and >3are dimensionless. Thus for >1, we have: MdLdTd = (M L. e T.)a (L)b ( L T. ) c .(M L. e T.) , since for dimensional homogeneity/consistency, A

has the unit of pressure. Evaluating: a= -1; b= 3; c= -1 so that: >1 = (T). e (d) ( Q). e .A = .d.A /uQ Similarly for others, we have: ?2 = L/d ?3 = d.Pin /uQ Therefore the nondimensional representation of the problem has the form: >1 = f( >2 , >3) Or d.A /TQ = f( L/d, d.Pin /TQ ) therefore: d.A /uQ = k1.dPin /uQ + k2.L/d ) or A = k1.Pin + k2.uQL/df (1') taking any two sets of data from table 6 and the data table 1 to solve for k 1 and k2 we have: 15157673=20684280k1 +135697.95k2 15157674=20684281k1 +135697.95k2 Thus k1=1; k2= -40.7273 Substituting into eq.16 A = Pin -40.7273 TQL/df (1") Finally to further link to the process parameters/ flow properties, let us expand and rearrange the term containing k2 in eq. 17, i.e 40.7273 TQL/df , as follows: Recall that for laminar flow under consideration, f=64/Re = 64/pvd/ T=64T/pvd T = fpvd/64 thus 40.7273fpvd/64(vA)L/df = 40.7273 fpvd/64 (>d/4)L/df = ( 40.7273/64 (>d/4)fpvL/d =0.4998 pvL/d =fpvL/d thus 40.7273.uQL/df = f pvL/d (18) which is the pipeline frictional pressure drop, <PL therefore A = Pin - <PL (19) Similarly for : f(B,u,,q,,,d) = 0, with a rank , r = 3, and thus only one nondimensional product we have > = (u)a (d)b ( Q)c .B thus for >1, we have: MdLdTd = (M L. e T.)a (L)b ( L T. ) c (M L. T.) , since for dimensional homogeneity/consistency, B has the unit of pressure/length solving: a = -1; b= 4; c = -1 thus > = (u). e (d)f ( Q). e .B = B.df /uQ Therefore the nondimensional representation of the problem has the form: >=k Or

B.df /uQ = k Therefore: k = df. B /uQ taking corrresponding sets of data from the table 16 and the data table 1 to solve for k we have: k = 40.73 thus, B = 40.73. uQ /df (%$) Finally to further link to the process paramters/ flow properties, recall that the RHS of eq.20 corresponds to that of eq 18 , with the omission of L thus by similar analogy, B = fpv / d (21) recall that f pvL/d, which is the total pipeline frictional ressure drop, <PL, thus fpv/d, will be the pipeline frictional pressure drop per unit length of pipe, that is, <PL/L therefore B = <PL/L (22) Finally, coefficient C is seen to vary only with length and in the same proportion. Thus C=L (23) substituting the values of A,B,and C from eqs 19, 20,21 into eq .15.and rearranging: Pout = Pin - <PL - <PL/L(L - X ){R}(1/AR - 1) (24) recall that Pin-Y is the difference between the inlet pressure and the exit pressure, or the measured pressure drop,for the total pipeline, <PX and R is the leakage/failure ratio, that is the fraction of the entering flowrate that leaked. therefore R = Qleak/Qin= Qin -Qout/Qin = 1- Qout/Qin where Qout is the flowrate at delivery point,L. making the above substitutions in eq.. We have ___E ___ = 1 + (1 V _E_)(Y)% _ *&# V 1' (25) which corresponds to the original equation 1. Thus only one equation with two unknowns, X and AR, describes the system. Note that in some problems, the above analysis would have yielded another equation such that the two variables will be determined by solving simultaneously. Howevever in this case with only one equation with two unknown, they have to be determined by numerical search techniques. 2.3.2 Numerical determinations of X/L and AR Numerous multivariable numerical search techniques have been devised for tackling cases as this(www.srl. a!e"h.e#u$e#u"a!ion$...$N%P-&n"ons!raine#-Mul!i'aria(le.pp! ). However to adapt/devise the appropriate one for each case requires proper expository look at the problem, by working from known to unknown to devise appropriate convergence scheme. Thus in this case, rearranging the original eq.1, : ___E ___ = 1 + (1 V _E_)(Y)0 1

)Y_ V 1: Where ___ = Pin Pout ___= frictional drop given by fpvL/d R is the ratio of quantity leaked to the entering flowrate, i.e R = Q leak/Qin = 1 Qout/Qin Thus by knowing the inlet and outlet flowrates ( Qin , Qout) and pressures(Pin, Pout),as well as an accurate estimate of the friction factor, f, the LHS can be evaluated. Thus the LHS is the known while the RHS is the unknown containing the two variables; X/L and AR(which lie between 0 and 1) to be determined., by any multivariable search technique ,like Powell, Fletcher algorithms(www.mpri.lsu.edu/textbook/Chapter6-b.htm ) or a new multivariable search method (Double Bisection Method) developed by the authors(unpublished ) 3. Discussion The problem associated with Leakage Detection Systems (LDS) is sensitivity-defined as the measure of the size of leak that a system is capable of detecting, and the time required for the system to issue an alarm in the event that a leak of that size should occur (api, 1995a). The relationship between leak size and the response time is dependent upon the nature of the LDS. Some systems manifest a strong correlation between leak size and the response time, while with others, response time is largely independent of leak size. Sensitivity will depend on the accuracy of the instrument. Accuracy is a measure of LDS performance related to estimation parameters such as leak flow rate, total volume lost, and leak location [API, 1995b].A system that estimates these parameters within an acceptable degree of tolerance, as defined by the pipeline controller/company, is considered to be accurate. Often times an LDS will use existing pipeline instrumentation such as flow meters and pressure transducers in their processes. The accuracy of these systems is evaluated in terms of the reliability and Robustness. Reliability is a measure of the ability of an LDS to render accurate decisions about the possible existence of a leak on a pipeline (API, 1995b). It is directly related to the probability of detecting a leak, given that a leak does in fact exist, and the probability of incorrectly declaring a leak, given that no leak has occurred. A system which incorrectly declares leaks is considered to be less reliable; however, if the system has the capability to use additional information to disqualify, limit, or inhibit an alarm, a high rate of leak declarations

may be considered less significant. Robustness is a measure of an LDSs ability to continue to function and provide useful information, even under changing conditions of pipeline operation (API, 1995b). A system is considered robust if it continues to perform its principle functions under less than ideal conditions. For this project, robustness is evaluated in terms of the capability of the LDS to distinguish between normal transient operating conditions and real leak events, and the ability to automatically make temporary system adjustments or disable certain leak detection functions as needed. Robustness is also evaluated in terms of the ability of an LDS to continue to perform in the event that an instrument is lost or goes off line (API, 1995b). Finally There is a great deal more to the cost of owning an LDS than the bare bones system price [i.e., the relative cost of instruments, maintenance or life cycle costs, and costs associated with adding more lines to the system]. For these reasons the costs associated with each technology are discussed only qualitatively. There are often tradeoffs between the price of an LDS and its performance. Highly effective systems [sensitive, accurate, reliable, and robust] ultimately will cost more to implement and maintain. It is up to the pipeline company to establish pipeline-specific performance standards and weigh the costs and benefits of an LDS That leaks still occur unnoticed can be explained in terms of the above parameters. For instance, current oil field units based on psi are hardly sensitive enough to detect small leaks. For instance, using eq.11 at AR=0.5, a leakage corresponding to one percent of the entering flow(i.e R=0.01) that occurs midway into the pipelength,will give an exit pressure reading of 15074773.6 Pa. the difference between this and no leakge normal reading(i.e R=0) of 15157672.7 Pa , shown in table 1. is 82899.1 Pa which in terms of oil field units of psi is just 12.023psi. this value can hardly be noticed on the measuring instrument due to its low sensitivity, unlike if it were in Pascals. Undetected, the crack(leakage area) increases due to fatigue and pressure. Fig1 shows the linear relationship between the exit pressure under varying R for the case of AR =0.5, if the AR is increased, the shapes of the graphs for different AR are shown in fig 4a,b,c

1#1#"'"*

1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* $ 1$$$$ %$$$$ *$$$$ &$$$$ #$$$$ e?it pressure9 Pa !ail length9 G !ig0>a7 e?it pressure vs fail length for '6 C )0HHHHHHHHHHHHH 4= $ 4= $-1 4= $-% 4= $-* 4= $-& 4= $-# 4= $-' 4= $-" 4= $-) 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* $ 1$$$$ %$$$$ *$$$$ &$$$$ #$$$$ e?it pressure9 Pa !ail length9 G !ig0>b7e?it pressure vs fail length for '6 C )0HHHHHHHHHHHHHH 4= $ 4= $-1 4= $-% 4= $-* 4= $-& 4= $-# 4= $-' 4= $-"

It shows that as the AR approaches 1, fluctuations in flow and hence exit pressure set in. These fluctuations generate shockwaves which will propagate, and if it reaches the sonic velocity (velocity of sound) results in explosion, which may or may not be accompanied by fire. Thus early detection of leakage is very important. 4. Conclusion Oil leakage have been part of oil industry operational problems, It normally occurs as a result of crack in the pipeline due to fatigue/corrosion and non-detection of it early enough, has compounded the problem,leading to progression into explosion/ spills and occasionally fire!, with the attendant huge costs and destruction. Thus in this paper, the authors have developed simple but efficient model for early prediction/detection of oil

leakage. The model is: ___E ___ = 1 + (1 V _E_)(Y)(1/)Y_ - 1) Where ___ = Pin Pout ___= frictional drop given by fpvL/d R is the ratio of quantity leaked to the entering flowrate, i.e R = Q leak/Qin = 1 Qout/Qin Thus by knowing the inlet and outlet flowrates ( Qin , Qout) and pressures(Pin, Pout),as well as an accurate estimate of the friction factor, f, the LHS can be evaluated. Thus the LHS is the known while the RHS is the unknown containing the two variables; _,( the leakage location) and )Y (the ratio of the pipe area to the leakage area) to be determined., by any multivariable search technique ,like Powell, Fletcher algorithms or a new multivariable search(Double Bisection Method) developed by the authors. Thus the oil leakage quantity, the location in the pipeline where it occurs (leakage point), and the extent of pipe damage (leakage area), can be determined by using the model. 6his /ill ensure early and prompt
remedial action that /ill minimiKe losses and damage occasioned by oil leaDs-

To ensure high sensitivity, accuracy, reliability and robustness, smaller units, like Pascals ,etc should be used to replace the current oil field units, like, psi, or simply incorporated as an adjunct.
1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* 1#1#"'"* $ 1$$$$ %$$$$ *$$$$ &$$$$ #$$$$ e?it pressure9 Pa !ail length9 G !ig0>"7e?it pressure vs fail length for '6 C )0HHHHHHHHHHHHHHH 4= $ 4= $-1 4= $-% 4= $-* 4= $-& 4= $-# 4= $-' 4= $-"

References
1- >merican ?etroleum <nstitute 2anual, 1((#b %- Chris Eze gM6A BncoGers 1il 5pill Arom 5hell ?ipeline g ;igeria ;e/s, 26 August 2013 *- +ode/it :ditor gNNPC confirms oil spillage at Ejigbo area of Lagos State gh Nigeria News, 6uesday, %", >ugust %$1* $#H%( &- httpHEEallafrica-comEstoriesE%$1*$)%'1$'*-html 5. ;1>> Oil Spill Case Histories 1967-1991, ,aKardous 2aterials and 4esponse 0iGision, 5eattle I>, '- "Oil Spill History". The Mariner Group. Retrieved 2008-11-02. 1((%

7.Perry & Green Perrys Chemical Engineers Handbook 7ed, McGraw-Hill, New York, 1999.

8. R. G. Rice; D.D. Do Applied Mathematics and Modeling for Chemical Engineers John Wiley & Sons, Inc. New York , 1995. 9. www.mpri.lsu.edu/textbook/Chapter6-b.htm 10. www.potto.org/FM/fluidMechanics.pdf 11. www.srl.gatech.edu/education/.../NLP-Unconstrained-Multivariable.ppt Nomenclature
Pin : inlet or departure pressure of oil: psi, pa Pout : exit or arrival pressure of oil: psi, pa

<P= pressure drop, <PL : total pressure drop due to friction across the pipelength; <PX: total pressure drop when there is aleakage at length, X of the pipeline, <P1= pressure drop upstream of the leakage point X, <P2= pressure drop downstream of the leakage point X, <P3= additional pressure drop due to leakage at point X. V= fluid velocity, ft/s, m/s Q= volumetric flowrate,bbl/d , ft3/s, m3/s, Qin= inflow ,Qout=outflow, Qleak=leakage flowrate T = fluid dynamic viscosity, Pa.s = = fluid density, lb/ft3, Kg/m3 R= ratio of inflow volumetric flowrate to the leakage flowrate = Q in/Qleak AR or AR : ratio of area of pipe to the leakage area
A = Aanning frictional factor

P-06 Production of Activated Carbon from Sugar Cane Bagasse *N. Salahudeen, C. S. Ajinomoh, M. Nuhu, S. O. Omagaand C. S. Akpaka Department of Chemical Engineering Ahmadu Bello University, Zaria *Corresponding author, email: nusdeen@yahoo.co.uk ABSTRACT Production of activated carbon from sugar cane bagasse was investigated. Zinc chloride was used as activating agent at varying ratios of 1:1, 0.75:1, 0.5:1 and 0.25:1 activating agent to bagasse, forming various formulations. The pH values of the various formulations were determined as 6.82, 6.84, 6.47 and 6.15 respectively. The ash content values were 38.7, 39.6, 40.8 and 41.6wt% respectively. The BET surface area values were 881.9, 801.2, 741.1 and 705.7 m 2/g respectively. Isotherm study was carried out usingFreundlich and Langmuir isotherms, Freundlich isotherm gave a better correlation. The best activated carbon formulation arrived was 1:1 AC. Key words: Absorbent, Activated carbon, Bagasse, Production, pH, Ash content, BET surface area, Freundlich isotherm, Langmuir isotherm. INTRODUCTION Activated carbon product has versatile areas of application in both industries as well as in household. Its production is basically through control pyrolysis at a varied temperature and impregnating reagent ratio. Recent trend in the production focused on utilizing the remains of agro-produce, which originally are considered as waste. Bagasse, a by-product from sugar cane processing, and traditionally used in firing the steam boiler of the evaporation unit of sugar processing plant, as feed for livestock farms, and in some instances are discarded on the field to decay. By composition bagasse account for over 65% of the remains after sugar extraction (Marshall etal., 2003). In most developing countries where sugar canes are produced, they are usually eaten raw and the

remains are allowed to liter the street. In Nigeria and particularly the northern region which account for a total annual output of 350,000 tonnes, over 70% of sugar being produced (NARC, 2011), such tremendous waste find their way into waste site. The bagasse like other cellulosic plant eventually degraded by the action of microorganism. Several works for developing high surface area activated carbon are going on (Pelekani etal., 2000) But the attractive part of the technology is by obtaining cheap source of raw material that will in long run leads to reduction in the overhead cost of production. Activated carbon (AC) as an absorbent has demonstrated to have wide area of application either in the industries or domestic and especially in gas purification (Gou etal., 2005), detoxification of effluent liquid or gas(Wu etal., 2006, Sivakumaretal., 2012,Mahamedetal., 2006), and as catalyst support (Ahmed etal., 2012) The presence of activated carbon as catalyst support modifies the structure and performance of the catalyst system. AC structure by pore size and the wall of the pore ranges from micro, macro, meso- pores, and eventually their distribution in a matrix depends on the source of the AC (Benaddietal., 2000). In some works (Tsegetal., 2005), it was related that the pore size distribution is further affected by the nature of the chemical activating agent employed during activation. The activating agents used consequently determine most of the properties of an AC such as the pore size, specific surface area, mechanical strength etc. (Salahudeen etal., 2012). Compare to other absorbent AC has several advantages, which includes its simplicity in operation and design of equipment, compatibility in removing large gamma of pollutants (Mudogaetal., 2008), low cost of its production since the raw material are abundantly available at little or no cost. Converting agro-waste such as bagasse to AC has only one impending factor which is high energy consumption. Hence, if the abundant gas being flared on daily bases in most refineries is channeled into AC production, this area of research will be very attractive. PROCEDURE Raw Material Collection and Treatment Sugarcane bagasse was collected from a sugarcane selling point in Samaru Zaria. The sugarcane bagasse was washed with tap wateruntil no more debris present. The washed sugarcane bagasse was sun dried for three days after which it was further dried to constant weight in an oven at 110 C. The dried sugarcane bagasse was crushed milled for 4 hrs using a ball milling machine. After milling the powder was sieved using a 32 mesh size sieve. Impregnation Process The powdered bagasse was impregnated with activating agent, zinc chloride at varying ratio of 1:1, 0.75:1, 0.5:1 and 0.25:1 of zinc chloride to bagasse, and then distilled water of 1000 wt% of the zinc chloride-bagasse mixturewas added, the mixture stirred thoroughly and heated at 100 C, for 2 hrs. to for a paste Activation Process Activated carbon (AC) was prepared by heating the paste prepared in a furnace at 700 C for 30 min. in carbon dioxide stream. The product obtained was crushed and washed with 0.1 M HCl solution and distilled water in order to remove residual zinc chloride and other impurities. Then the product was dried at 105 C for 6 hours in an oven pH Determination The samples pH values were determined using the ASTM 3838-80 standard: 10g of the AC prepared was heated in 100 ml distilled water to boiling point for 15 min. The slurry formed was filtered using filter paper, then the filtrate was cooled to 50 C and the pH was measured using a

pH meter. Ash Content Determination The ash content of the various AC prepared were determined using the ASTM D2866-94 standard: the AC sample was heated in a crucible to constant ash weight at 650 C. The resulting ash was weighted and the ash content of the AC was evaluated using Equation (1) below. Total ash (%) = x 100 (1) Where B = weight of empty crucible B = weight of crucible plus AC before heating B = weight of crucible plus ash after heating Isotherm Study The adsorption capacity of the various AC prepared were determined using 10 ppm stock solution of phenol as the absorbate solution. 40 ml of the phenol solution was poured into each of five Erlenmeyer flasks containing 0.03, 0.05, 0.08, 0.1 and 0.13g of a specific AC formulation. The flasks were mechanically shaken for nine days after which the solutions were filtered using filter paper. The phenol remaining in solution was measured using UV spectrophotometer at a wavelength of 269 nm. The adsorption data generated were analyzed using theFreundlichand Langmuir Adsorption Isotherm equations. Freundlich isotherm equation is as presented in Equation (2a-b). qe= KCe 1/n (2a) logqe = log K + 1/nlogCe (2b) Where qis the amount of absorbate adsorbed per unit mass of adsorbent at equilibrium (mg/g). Ce is the equilibrium concentration of the absorbate (mg/L). K and n are Freundlich constants with n giving anindication of how favorable the adsorption process. Value of n in the range between 1 and 10 denotes favorable adsorption. Langmuir isotherm equation is as presented in Equation (2c-d). (2c) (2d) Where qe is the amount of absorbate adsorbed per unit mass of adsorbent at equilibrium (mg/g), qm the maximum adsorption capacity corresponding to complete monolayer coverage on the surface (mg/g), Ce the concentration of absorbate at equilibrium (mg/L) and b is a constant related to the affinity of the binding sites (L/mg). Specific Surface Area Determination The specific surface area was determined using an adapted BET method (Salahudeen etal., 2012) which employs adsorption of absorbate (water molecules) on the surface of the adsorbent (samples to be characterized) using the BET theory. The resulting BET equation is expressed by Equation (3). @A (3) In this method an absorbate constant relative humidity was established as the relative humidity of water vapour obtained from a saturated salt solution in water. This relative humidity was proved to be equal to P/Po in Equation (3). The procedure is by preparing two saturated solutions of a particular salt, one was kept in an air tight desiccator and the other was exposed to air in the laboratory.The two were left for 24 hr., noting their respective weight at the beginning and at the end of 24 h. The relative humidity of the saturated salt solution was evaluated as the ratio of the weight differences of salt solution in desiccator (at initial point and after 24 h) to the weight differences of salt solution left open (at initial point and after 24 h). Four salts were used, they

included; CaSO4, K2SO4, CH3COONa, MgCl2. After determining the value of P/Po for each salt, a saturated solution of the salt was prepared and kept in an air tight desiccator with a 1.0 g quantity of the adsorbent evenly spread on a Petri dish and kept together with the saturated salt solution in the air tight desiccator for 24 h maintaining the laboratory temperature at room temperature. The weight gain of the sample determined at the end of the 24 h was used to represent V in Equation (3). Being an improvised method this method of determining of BET surface area is prone to some error, the error correction factor as determined by (Salahudeen etal., 2012) was 0.8017. RESULTS AND DISCUSSION Table 1.pH and ash content determined for the various AC formulated Sample pH Value Ash Content (wt%) 1:1 6.82 38.7 0.75:1 6.64 39.6 0.5:1 6.47 40.8 0.25:1 6.15 41.6 Table 2.Data generated for evaluation of the relative humidity of the salts used for in the BET characterization SALT MgCl2 CaSO4 CH3COONa K2SO4 QD1 22.698 24.291 30.973 35.825 QD2 22.632 24.273 30.652 35.621 QO1 20.218 22.465 27.326 32.359 QO2 16.192 21.127 21.127 25.212 RH 0.01639 0.0035 0.05178 0.02854 Where (4) Where RH = (P/Po) (5) Where, QD1 and QD1 = Initial and final weight of salt solution in desiccators respectively. QO1 and QO2 = Initial and final weight of salt solution open to room condition respectively.
y = *-))'*3 + $-$1(* 4R = $-()#* $ $-$# $-1 $-1# $-% $-%# $-* $ $-$% $-$& $-$' $-$) I $g1(% 6< y = &-%()*3 + $-$$$# 4R = $-(()( $ $-$# $-1 $-1# $-% $-%# $-* $ $-$% $-$& $-$' $-$) I $g1(%

6<

Figure 2. BET curve Figure 1. BET curve for 1:1 AC for 0.75:1 AC Figure 3. BET curve for 0.5:1 AC Table 3. Measured BET values of the various activated carbon formulated Sample Specific Surface Area Determined(m2/g) Actual Specific Surface Area (m2/g) 1:1 1100.0 881.9 0.75:1 999.4 801.2 0.5:1 924.4 741.1 0.25:1 880.2 705.7 Table 4.Isotherm datafor the various sample types Activated Carbon Loading (g) Phenol absorbed (mg)/Sample Type 1:1 0.75:1 0.5:1 0.25:1 0.03 0.20 0.16 0.14 0.08 0.05 0.23 0.20 0.15 0.1 0.08 0.27 0.24 0.17 0.11 0.10 0.30 0.26 0.19 0.13 0.13 0.32 0.28 0.24 0.17
y = &-'&)*3 F $-$$1% 4R = $-(((* $ $-$# $-1 $-1# $-% $-%# $-* $ $-$% $-$& $-$' $-$) I $g1(% 6< y = &-))113 F $-$$1* 4R = $-(((* $ $-$# $-1 $-1# $-% $-%# $-* $-*# $ $-$% $-$& $-$' $-$) I $g1(% 6<

Figure 4. BET curve for 0.25:1 AC Figure 5.Freundlich curve for 1:1 AC Figure 7.Freundlich curve for 0.75:1 AC
y = $-))#&3 + $-11')

4R = $-()&& $ $-1 $-% $-* $-& $-# $-' $-" $-) $ $-% $-& $-' $-) .og J .og Ce y = $-$%'"3 + $-")&& 4R = $-*('% $-) $-)% $-)& $-)' $-)) $-( $-(% $-(& $%&' CeKJe Ce y = 1-%(%"3 F $-%($" 4R = $-((#" $ $-1 $-% $-* $-& $-# $-' $-" $-) $ $-% $-& $-' $-) 1 .og J .og Ce y = F$-$)'%3 + 1-''$* 4R = $-("$' $ $-% $-& $-' $-) 1 1-% 1-& 1-' $%&') CeKJe Ce

Figure 6. Langmuir curve for 1:1 AC Figure 8. Langmuir curve for 0.75:1 AC Figure 9.Freundlich curve for 0.5:1 AC

Figure 11.Freundlich curve for 0.25:1 AC Table 5.Isotherm parameters determined for the various AC formulations Sample Freudlich Langmuir n K R2 b R2 1:1 1.0 1.20 0.984 0.033 0.396 0.75:1 0.8 0.51 0.995 -0.052 0.970 0.5:1 0.7 0.19 0.574 -0.064 0.154 0.25:1 0.5 0.04 0.598 -0.069 0.258
y = 1-#*')3 F $-"*$' 4R = $-#"&% $ $-1 $-% $-* $-& $-# $-' $-" $-) $ $-% $-& $-' $-) 1 .og J .og Ce y = F$-%%$*3 + *-&&&( 4R = $-1#& $ $-# 1 1-# % %-# * $%&') CeKJe Ce y = 1-('*(3 F 1-&&1* 4R = $-#()* $ $-$# $-1 $-1# $-% $-%# $-* $-*# $-& $-&# $-"# $-) $-)# $-( $-(# .og J .og Ce y = F$-#"#3 + )-*"' 4R = $-%#)& $ 1 % * &

# ' $ % & ' ) 1$ CeKJe Ce

Figure 12. Langmuir curve for 0.25:1 AC Figure 10. Langmuir curve for 0.5:1 AC DISCUSSION OF RESULTS The pH values of the various activated carbon produced were generally slightly acidic with the acidity increasing with decrease in the wt % composition of the activating agent, similarly, the ash content of the samples also increased with decrease in the wt % composition of the activating agent as can be seen from Table 1.This means that the more thewt % composition of the activating agent, the more transformed was the carboneousbagasse to the less carboneous activating agent and the more acidic and oxidizing the material becomes.The BET specific surface area of the activated carbonproduced were generally high, however, a regular trend of increase in the specific surface area values was observed withincrease in wt % composition of the activating agent, however, the highest value of 881.9 m2/g was observed for the 1:1 sample as shown in Table 3.The adsorption capacity analysis carried out showed that Freundlich isotherm gave a better correlation since all its parameters were positive across all the various formulation, while in the case of Langmuir the parameter was generally negative except for 1:1 AC which was positive. Hence, negative or too low parameter implies poor correlation. Moreover, the R2 values for the Freundlich isotherm were relatively higher than that of the Langmuir isotherm. The 1:1 AC formulation showed the best correlation with the Freundlich isotherm since the higher the n and Kvalues the more the adsorption capacity of the material. As can be seen from Table 5, 1:1 AChad n and K parameters of 1.0 and 1.2 respectively,while the other samplesgenerally had lower n and K values. Though 0.75:1 AC had the highest R 2 value;0.995, as shown in Figure 7, slightly higher than that of 1:1 AC; 0.984 as shown in Figure 5,butthe 1:1 AC still remains the best adsorbent having the highest n and K values. However, the 0.5:1 and 0.25:1 AC showed poor correlation with the Freundlich isotherm having R 2 values of 0.574 and 0.598 respectively as shown in Figures 9 and 11 respectively and both had very low n and K parameter indicating that they had poor adsorption capacity. CONCLUSION Using 1:1 zinc chloride to sugarcane bagasse activation ratio a good activated carbon with thehighest adsorption capacity of 6.67 mg/g phenol adsorption and 5.00 mg/L equilibrium phenol concentration at 0.03 g loading of the activated carbon. This activation ratio also showed the highest specific surface area of 881.9 m2/g, comparable with otherpast works (Mudogaetal., 2008). For the other activation ratios;0.75:1 also produced activated carbon with fairly good adsorption capacity and good surface area, however, the 0.5:1 and 0.25:1 samples showed very poor adsorption capacity and low surface area.

References
A. S. Ahmed, N. Salahudeen, C. S. Ajinomoh, H. Hamza, A. Ohikere, 2012. Studies on the Mineral and Chemical Characteristics of PindigaBentonitic Clay. Petroleum Technology Development Journal. 1(1): 56-63. C. Ng, W. E. Marshall, R. M. Rao, R. R. Bansode, J. N. Losso, 2003. Agronomic Potential of Reseda Luteola L. as New Crop for Natural Dye in Textile Production. Ind. Crops Prod. 17(3): 199-207. C. Pelekani, and V. L. Snoeyink, 2000. Competitive Adsorption between Atrazine and

Methylene Blue on Activated Carbon: the Importance of Pore Size Distribution. Carbon.38(10): 23-36. F. C. Wu, R. L. Tseng, 2006. Preparation of Highly Porous Carbon from Fir Wood by KOH Etching and CO2 Gasification for Adsorption of Dyes and Phenols from Water.Colloid Interface Sci. 294: 21-30. F. S. Mahamed, W. A. Khater, M. R. Mostafa, 2006. Characterization and Phenol Sorption Properties of Carbon Activated by Sulphuric Acid. Chem. Eng. J. 116: 47-55. H. Benaddi, T. J. Bandosz, J. Jageillo, J. A. Schwarz, J. N. Rouzaud, 2000. Surface Functionality and Porosity of Activated Carbons Obtained from Chemical Activation of Wood. J. Carbon. 38: 669-674. H. L, Mudoga, H. K. Yucel, N. S. Bioresour, 2008 Decolourization of Sugar Syrups Using Commercial and Sugar Beet Pulp Based Activated Carbons. Technol.. 99: 3528 3533. J. W. S. Gou, Y. L. Xu, A. J. Lua, 2005. Adsorption of NH 3 onto Activated Carbon Prepared from Palm Shells Impregnated with H2SO4. Colloid Interface Sc. 281: 285-290. N. Salahudeen, A. S. Ahmed, C. S. Ajinomoh, and H. Hamza, 2012. Surface Area Enhancement of PindigaBentonitic Clay for Usage as Catalytic Support. Petroleum Technology Development Journal. 1(2): 65-73. R. L Tseg, F. C. Wu, R. ShinJuang, 2005. Comparison of Porous and Adsorptive of Carbon Activated by Steam and KOH.J. Colloid Interface Sci. 283(1): 49-56. V. Sivakumar, M. Asaithambi and P. Sivakumar, 2012. Physico-chemical and Adsorption Studies of Activated Carbon from Agricultural Wastes.Advances in Applied Science Research. 3(1): 219-226. Nigerian Agro-industrial Research Commission. Annual workshop 2011. P-07 Extension of Heat Pump/Heat Engine Principles to Distillation Column Analysis Olakunle, M.S.a,1, Adefila, S.S.b,2, Olawale, A.S.c,3 and Bugaje, I.M.d,4 a,cDepartment of Chemical Engineering, Ahmadu Bello University, Zaria, Nigeria bDepartment of Chemical and Petroleum Engineering, Covenant University, Ota, Nigeria dNational Research Institute for Chemical Technology (NARICT), Zaria, Nigeria. 1msolakunle@abu.edu.ng, 2samadefila@gmail.com, 3asolawale@yahoo.com, 4idrismbugaje@yahoo.com Abstract A 10-staged conventional binary distillation (using ethanol/water system) operation was analyzed with thermodynamic principles in this work. Use was made of the temperature, composition and enthalpy profiles obtained from the converged simulation of distillation operations obtained from the Aspen Plus and Aspen Hysys simulators. Since all processes in nature are essentially composites of heat/work/chemical potential inter-conversions (consuming/generating), an extension of the application of the simple heat pump/heat engine analysis, to the analysis of distillation operation was also investigated. Whereas a distillation column is a heat engine on a global and stand-alone basis, the plate-to-plate distillation operation was seen to be akin to the operation of a reverse absorption heat pump. A similar Chebyshev X,Y Rational Order 5/6 model equation was found to represent the two operation very well, with residual errors ranging between 1.5% for the absorption heat pump operation model and 3.5 for the distillation operation model using the binary ethanol/water system. Keywords: Absorption heat pump, distillation, co-efficient of performance, analysis by analogy

1.0 Introduction Distillation process has over the years been faced with the problems of large intensive energy utilization (US DOE, 1984, Ognisty, 1995), and there has being an endless quest towards improving the economics of the process since the beginning of the Industry due to the enormous amount of energy utilization and significant capital outlay it requires. Various options are currently being explored in the quest towards energy conservation and recovery (Demirel 2004,2006; Pinto et.al 2011). Optimization techniques, like pinch and exergy analyses have been developed by several researchers (Dhole and Linnhoff, 1993; Rashad and El Maihy, 2009; Yuelong et.al 2010; Vuckovic et.al, 2012) to tackle this high energy utilization problem, but still the thermal efficiencies of stand-alone distillation columns (DCs) are still found to be low (Cengel and Boles, 2007). The overall operation of a DC succinctly represents that of a heat engine (Ognisty, 1995) and the concurrent plate to plate operation of the DC could be likened to the operation of an absorption heat pump. Heat pump refers to a device which raises the quality (potential) of heat energy from a low temperature level to heat energy at a higher temperature level using a relatively small quantity of high grade energy (HGE). Thermodynamic analysis and theoretical basis for improvement of efficiency thus suggests that an extension of the principles of heat pump/heat engine to DCs can lead to simple and relatively more efficient means of analyzing the latter. The success of the extension of simple cycles of heat engine (transformation of heat to work) and heat pump (transformation of high grade energy to heat) can open up the extension of simple to complex processes. The combination of basic theories of transformation of energy from one form to another and their subjection to corresponding combination of simple thermodynamic analysis to complex models can thus help in their analysis. Olawale (2006) developed simplified generalized performance equations for vapour compression heat pumps analysis. The models proved to be very useful in the simplified analysis of heat pump systems. On a general outlook, most thermal systems are either work requiring or work producing, as obtained in heat pump and heat engine respectively (Cengel and Boles, 2007). Conceptually, the application of the principles of heat pump/heat engine cycles and their analyses can lend a useful understanding to many of the black-boxes that exist in these thermal systems (Dhole and Linnhoff, 1993) and aid their easy and simplified analysis. Holland et al (1981) have presented extensive literature of various energy cycles within the heat pump system, while Adefila (1983) and Bugaje (1987) had discussed a very detailed classification of heat pumps and their corresponding analysis. In absorption heat pumps (AHP), Figure 1, an expansion valve is used for the expansion from condensing to evaporating pressure. However, the compression process, and thus the addition of primary energy, is achieved by a thermodynamic system without a mechanical compressor. The drive of the AHP consists of a circuit in which the working fluid is absorbed by an absorbent at a lower pressure and is separated again from it, by adding heat, at a higher pressure and returns into the normal heat pump cycle. The only mechanical driven component in the circuit is the solution pump. After evaporation, the working fluid is absorbed by the absorbent in the absorber accompanied by a rejection of heat QAB to the surroundings. In this mixture, the evaporator pressure becomes the partial pressure of the working fluid. The enriched solution is compressed to the pressure in the generator by a pump and heated to a temperature TGE. At the higher temperature, the

solubility of the working fluid in the absorbent is appreciably smaller, and the heat received QGE results in the removal of the vapour (working fluid) from solution. The working fluid, now separated from the solution, passes to the condenser. The depleted solution is expanded to the pressure of the absorber by an expansion valve and can now again absorb working fluid. The Coefficient of Performance (COP) for the conventional absorption heat pump, depending on the targeted effect, can be written as:

( ) ( ) GE
CO AHA Q

QQ COP AB + = for heating 1

and (
EV

) ( ) GE

ACLA Q

Q COP = for cooling 2 Comparison of the actual COP can be made with the theoretical Carnot efficiency. Figure 2, a schematic of a Carnot absorption heat pump viewed as composing of a Carnot heat engine, on the right hand side, and a reversed Carnot heat engine (Carnot heat pump) on the left hand side.
Generator

Condenser Absorber
Evaporator Economizer Expansion valve (TCO TEV) (TAB TEV)

PEV = PAB TCO = TGE QCO QEV QAB QGE Figure 1. A Conventional Absorption Heat Pump
Solution pump

According to the cycle, the minimum amount of work W, required to operate a heat pump for cooling, at an absolute temperature of TEV, when ambient temperature is TCO is
QEV TEV TCO TEV W

 =3

Likewise, the minimum quantity of heat energy required to contain an amount of work W, in a Carnot heat engine is,
W AB TGE T TGE GE Q =4

Consequently, the quantity of heat at the high temperature TGE required to effect a cooling capacity of QEV is obtained by combining Equations 3 and 4 to give,
= AB TGE T TGE GE Q Q EV

TEV TCO TEV 5

Thus, with reference to Equation 5, the COP for the heating mode is given as,

()1
- TEV CO T TGE TAB GE T EV

T COP AH + =6

Adefila (1983) derived a pseudo-ideal model for calculating the maximum obtainable COP for the heating mode of a high temperature CAHP system. The (COP)AHMO is equivalent to Rankine (COP) in vapour compression heat pump systems, and the mathematical relation between (COP)AHMO and the absorbent and working fluid in the system found through mass and energy balances as shown in Figure 3 is given as

()
( )(

) ( )( ) FR H5 H10 H1 H5
H4 H7 FR H7 H8 H1 H3 COP AHMO + ++ =7

where,
()

() ( ) ( ) XGE XAB
XGE W5X W 10 X W51X FR = =

8 where XAB, XGE are weight percent of solute in solution in the absorber and generator respectively and XW if fractional weight of working fluid in solution. The application of the phase rule shows that (COP)AHMO = (COP)AHMO ((FR), TCO) 9 However, the thermodynamic compressor is composite. This is partially elucidated by Equation 8 which shows (FR) to be a function of the absolute concentration of the working fluid mixture in the generator and absorber, and the concentration width. In fact, a more useful form of this Equation is (FR) = (FR) (TGE, PCO/PEV) 10

or (FR) = (FR) (TAB, PEV, PCO/PEV) 11 TCO TEV QEV QCO QGE QAB TAB TGE WW Figure 2: Carnot Absorption Cycle Principle These expanded equations present very useful basic parameters for the design, evaluation or control of the absorption heat pump system. 3.0 METHODOLOGY 3.1 Analysis by Analogy A cursory look at the plate-to-plate operation of the distillation process and that of the conventional absorption heat pump was critically considered via analysis by analogy to establish the similarities of operations between the two systems. The simultaneous vapourization and condensation processes of the plate-to-plate distillation operation was theoretically compared with the vapourization/absorption and evaporation/condensation processes of the conventional absorption heat pump using the description of the processes shown in Figures 3 and 4. In the conventional absorption heat pump, the absorber/evaporator units are at the same pressure, likewise the condenser/generator combination, though at relatively higher pressure. Thus the generator and the absorber are at different pressure level; this pressure difference is equilibrated by the presence of the solution pump and the expansion valve which are fixed between the absorber and the generator. 3.2 Performance evaluation and modelling of a conventional absorption heat pump and distillation operation. The process flow diagram (PFD) of a conventional absorption heat pump (CAHP) system was set-up as shown in Figure 3 using the Aspen Hysys process simulator. In Figure 5, the absorber of a practical CAHP was conceived to be a combination of a mixer and a cooler. This is so because in the absorber of a practical CAHP, both mixing and condensation processes occur, hence the display of absorber mixer and absorber cooler. Similarly, the generator of a practical CAHP also has both heating and rectification processes occurring within it. This PFD was then used to generate process data for the streams shown in the PFD, which were used to calculate the enthalpies of all the streams in the cycle. Assumptions made in the simulation. The stream no. 2 leaving the rectifier into the condenser was taken to be superheated vapour which possesses high grade energy for delivery in the condenser. The stream no. 5 leaving the evaporator into the absorber was taken to be saturated vapour. This represent the pseudo-ideal condition for the exit stream from the evaporator.
Distillation
2

1 78 69 5 10 Figure 3: Conventional Absorption Heat Pump 8 75 4 32 1 10 Figure 4: Plate-to-Plate Distillation Operation

Lean solution Lean solution

QLIQU QVAPU QLIQL QVAPL

The simulation runs were limited to a composition range of the working fluid/absorbent (ethanol/water) pair of 0.5 and 0.75 and a temperature range of between 600 and 800C. At mixture composition and temperature higher than these, separation would not be effective since ethanol/water mixture forms azeotrope at temperatures above 800C. The stream no. 3 leaving the condenser into the expander was taken to be saturated liquid. The temperature and pressure conditions in the condenser and the evaporator were taken to be constant, hence phase changes from vapour to liquid and from liquid to saturated vapour take place in these units respectively. Vapour inlet to the solution pump was avoided. The pressure in the generator and the condenser were taken to be the same. Likewise, the pressure in the absorber and the evaporator were the same. The calculated mass enthalpies were then used to determine the maximum obtainable coefficient of performance (COPAHMO) of the system for each runs of the simulated process using the expression of Equations 7 and 8, modified as in Equations 12 and 13 respectively. 1COP2$!(OB
!C-!1.D _-R__!1.-!E_D !.-!6 _-R__!1F-!G_D !.-!1F

12 where _-R_B
1- _H5_1F _H5_G- _H5_1F

B
H3E H3ED H$B

13 where XAB, XGE are weight percent of solute in solution in the absorber and generator respectively and XW is fractional weight of working fluid in solution. FR is the fluid ratio. Aspen-Hysys simulator was also used to simulate a distillation operation for ethanol -water binary system in order to generate data for modelling the distillation operation. The conditions used for the simulation of the distillation operation are as given in Table 2. Several simulation runs were undertaken varying the feed composition from 0.1 to 0.9 ethanol mole fraction. The data generated were used to a develop model which was compared with that for the CAHP for its easy extension for the analysis of distillation operation. The effect of the feed stream temperature on the COP equivalent of the distillation column were also estimated from the data

based on the comparison between the distillation operation and the conventional absorption heat pump system. Figure 5: Schematic of a Conventional Absorption Heat Pump Table 2: Distillation Operating Conditions S/No. Parameters Simulation Value 1 Number of Stages 10 2 Feed Rate, litre/s 9.5 x 10-4 3 Feed Rate, mol/s 0.04161 4 Feed Pressure, 105 Pa 1.01325 5 Feed Temperature, K 302.45 6 Feed Stage 5 7 Condenser Pressure, 105 Pa 1.0111 8 Pressure Drop, Stage 2-10, Pa 980 9 Distillate Rate, mol/s 0.00205 10 Reflux Ratio 5 11 Feed Mole Fraction 0.1 12 Condenser Type Total 4.0 RESULTS AND DISCUSSION 4.1 Analysis by Analogy The theory of absorption heat pumps is based on thermodynamics of solution, likewise that of distillation. In binary mixtures, each condition of state is determined by three parameters: pressure (P), temperature (T) and solution concentration (XW) in weight fraction of working fluid. A deeper look at the various operations within the units that constitute the absorption heat pump (i.e the vapourization/absorption processes of the thermodynamic solution circuit of the generator/absorber unit, and the evaporation/condensation processes of the vapour flow of the evaporator/condenser unit) is very much akin to the simultaneous vapourization/condensation processes of the plate-to-plate distillation operations. Table 3 illustrates the comparative description of the components and processes between the two systems. The vapourization process (in the generator) and the condensation process (in the absorber) of the thermodynamic solution circuit in the CAHP system (shown in the envelope of Figure 3) actually mimic the simultaneous vapourization and condensation processes of the plate-to-plate operation in a distillation column. Whereas the evaporation and condensation processes of the evaporator and the condenser of the CAHP are subsumed in the upper plate vapourization and condensation processes of the distillation operation. Table 3: Comparative Description of the Components and Processes of the Conventional Absorption Heat Pump and the Plate Distillation Operation S/N Unit\System Absorption Heat Pump Distillation Operation 1 Generator Vapourization process takes place in the generator in an absorption heat pump system. The rich solution (10) rising from the absorber through the solution pump and the economizer is heated by the high grade energy

QGE supplied to the generator. The more volatile component (1) of the rich solution is vapourized leaving a lean solution (5) which is returned back to the absorber via an expander for another The reboiler of the distillation column is akin to the generator. On a plate-toplate consideration, the lower plate serves as the generator, because it is present at a higher energy value due to the high grade energy, QVAPL vapour entering the plate from the reboiler. The more volatile component of the liquid mixture (10) flowing down the downcomer of the column is vapourized by the high grade energy vapour. The vapourized component (1) then rises up the column to vapour intake. increase the composition of the more volatile component on the upper plate, and also provide the work energy needed for the component separation on that plate 2 Absorber Condensation process takes place in the absorber. The lean solution (5) flows from the generator through the economizer (6) and the expander (7) takes up the vapour from the evaporator (4) thereby producing a rich solution (8) that is pumped to the generator via the economizer. The condensation process releases the heat of condensation and mixing QAB. This heat of mixing is often reflected in the temperature value of the exiting rich solution (8) as determined by the Cp values of the mixing streams A lean solution (5) on the plate flows to the downcomer (7) where it then flows downward to a lower plate for

vapour intake. This lean solution mixes with the vapour rising from a lower plate causing condensation of that vapour stream, thereby releasing the heat of mixing, QLIQL. The condensing and evaporating processes are both subsumed in the upper plates of the distillation column. The upper plate of an equilibrium staged-column serves as the condenser in that it receives the vapour coming from the reboiler (i.e. lower plate in this case). As the vapour enters the plate, it mixes with the liquid on that plate and condenses by losing heat Q which is used to perform the work of separation on that plate. Since there is simultaneous condensation and vapourization on the plate. Likewise, the evaporator is also subsumed in the upper plate, probably in the vapourization unit of the upper plate. Here, QLIQU, a lower grade energy compared to QCOLL, is supplied by the lean solution flowing into that plate from an upper plate. This energy is used to vapourize some of the more volatile component on the plate, which does increase the purity of the vapour component. 3 Condenser The vapour from the generator (1) is condensed. The high grade energy QCO from this condensation process could be used to heat up process stream, which is a type of fluid work done. The low grade vapour (2) emanating from the unit is then expanded and flows to the evaporator 4 Evaporator The low pressure, low grade heat vapour stream (3) flows into the evaporator, where it absorbs low grade energy QEV that slightly

raises its energy to a condition for the absorber intake of the vapour (4). It follows therefore that compared to the CAHP system, the distillation operation would be expected to give a higher efficiency in terms of energy utilization. This is due to the absence of the hardware components of the condenser, the solution pump, the economizer and the evaporator, which on their own introduces additional irreversibility to the entire process. The low pressure liquid stream flowing downwards from an upper plate possesses kinetic energy and hydrostatic head with which it upgrade its low pressure to that of the incoming high pressure vapour stream flowing upward from the plate beneath. With the pressure balance on the plate, proper mixing of the vapour and liquid streams is achieved. Concurrently, the effective collapse of the vapour droplets into liquid during condensation and the sudden volume expansion due to vapourization of liquid molecule, like the tsunami effect, also contribute to make the mixing very effective. This effective mixing therefore brings the liquid and vapour streams on the plate into intimate contact creating opportunity for mass and energy transfer as a result of the 1-#% 1-#& 1-#' 1-#) 1-' 1-'% 1-'& "* "# "" "( )1 COP'<MO Generator &emperature9 &GE )C
]` ]` ]` ]` ]` 64:+ 64:+ 64:+ 64:+ 64:+ of of of of of '$ '# "$ "# )$ +] +] +] + +]

concentration and energy gradients between the mixing streams. During mixing both heat of mixing and heat of condensation, a type of QAB and QCO are generated, which are probably used to vapourize the most volatile component (MVC) of the liquid stream. The vapourization of the MVC from the liquid stream brings about separation on that plate. This operation continues up the column giving rise to a vapour stream that gets richer in the MVC, while the liquid flowing downwards gets leaner in the MVC. From the foregoing therefore, the processes of vapourization and absorption in the CAHP system are comparable to the plate-to-plate operation of the distillation process, the already developed and established models of the CAHP system can therefore be extended to analyze the performance of distillation operation. In the CAHP, the major objectives are the cooling and heating effect of the system, hence the calculation of coefficient of performance for both cooling (COPCL) and heating (COPH) respectively. However, since the condenser/evaporator processes of the vapour unit of the CAHP system is subsumed in the upper plate of a distillation operation, the high grade energy intake of the generator as in the reboiler, (akin to a lower plate (of high P and T) of a distillation operation) could only have been used to delivered energy that would have been used to effect

separation. From the comparison in Table 3 therefore, it can be seen that: QGE =QVAPL HGE associated with the vapour from the lower plate QAB = QLIQL Heat energy associated with the liquid from the lower plate QCO = QVAPU Heat energy associated with the vapour from the upper plate QEV = QLIQU Heat energy associated with the liquid from the upper plate The (COP)AHMO model equation of the CAHP system is therefore the most suitable model applicable to plate-to-plate distillation operation. 4.2 Performance evaluation and modelling of a conventional absorption heat pump and distillation operation. The results of the effect of generator temperature on the COPAHMO of a CAHP using ethanolwater pair evaluated at different rectifier temperature and molar composition of the ethanol are as shown in Figures 6 and 7. Figure 6: COPAHMO versus TGE at different TREC TGE is the average temperature of all the streams involved in the vapour generating processes of the generator unit. Similarly, the condenser temperature, TCO is the average temperature of the streams linked to the condenser. The corresponding temperature lift, TLIFT, for these plots is approximately 31.30, while the evaporator temperature, TEV was 470C. The concentration gap varies between 0.06 and 0.165. A look at Figure 6 shows that the performance of the CAHP increases with increase in TGE, irrespective of the rectifier entrance temperature. A maximum
1-#% 1-#& 1-#' 1-#) 1-' 1-'% 1-'& "* "& "# "' "" ") "( )$ )1 COP'<MO Generator &emperature9 &GE )C
]` ]` ]` ]` ]` ]` $-#Y $-##Y $-'Y $-'#Y $-"Y $-"#Y

COPAHMO value of about 1.6309 is attained at TREC of 700C, which suggest the optimum condition to operate the CAHP system. All the plots followed the same trend in which there was an increase in COPAHMO with slight increase in TGE, which continue until it reaches a maximum and then begin to diminish. Thus beyond this maximum points, operating the system at higher TGE will no longer be economical, as higher grade energy supplied to the generator will yield a lesser output of the delivered heat at the condenser. Figure 7: COPAHMO versus TGE at different ethanol/water Mole Fraction Figure 7 show the plot of COPAHMO versus TGE but at different values of the molar composition of the working fluid/absorbent mixture. It could be seen that operating the system at 0.55 molar composition of the mixture will deliver the best performance. Below and above this will also not be economical in terms of performance for the system. However a similar trend of the plots was

observed in which there was a little increase in the performance of the system as the TGE increases until it peaked at about TGE of 780C before a diminishing returns sets in. This suggests that the optimal TGE would be 780C beyond which the process would be uneconomical. The COPAHMO values peaked at a mole fraction of the ethanol/water system of 0.55 and then declined on higher molar fraction. Thus, the 0.55 mole fraction of the ethanol/ water mixture will yield the most economical COPAHMO. This observation for the ethanol/water system of the CAHP operation agrees with literature data in which Adefila (1983) presented the graph of COPAHMO versus TGE for LiBr/H2O CAHP system, in which a similar trend was obtained. Models developed provide an easy extension of the heat pump/heat engine principle to distillation operation, based on earlier comparison between the two systems. The first model developed for CAHP was that which relates the concentration gap DX of the solution unit as a function of stream enthalpies (H2 and H5), Equation 14. _=
_ _______ _ 7______ _____ ______ ______ \_____ _______ ______ _______ _______ _____ ]______ (_)___ _______ ______ !______ Y_____ ___)____ _______ ______ Z______ [_____

14 where Z = DX, x = H5 and y = H2 Figures 8 shows the parity and residual plots and the parameter values for the compositional changes (DX) model for the absorption heat pump working on ethanol-water binary mixture. The model developed for the distillation operation is as shown in Equation 15. The model is a Chebyshev X,Y Rational Order 5/6, a type of [DX = f(HA,hA)] like Equation 14. z=
a + dT1_x'_ + eT1_y'_ + hT2_x'_ + iT2_y'_ + lT3_x'_ + mT3_y'_ + pT4_x'_ + qT4_y'_ + tT5_x'_ + uT5_y'_ 1 + bT1_x'_ + cT1_y'_ + fT2_x'_ + gT2_y'_ + jT3_x'_ + kT3_y'_ + nT4_x'_ + oT4_y'_ + rT5_x'_ + sT5_y'_ + vT6_x'_ + aaT6_y'_

15 The selection of the variables for the models were based on the earlier comparison between the CAHP and the distillation column, (Figures 3 and 4 and Table 3). Model equation relating concentration gap DX as a function of stream enthalpies (H2 and H5) developed for the CAHP (Equation 14) has a coefficient of determination, r2 of 0.9948, a fit standard error of 0.00528 and F-Stat value of 61.3194. These are good statistical values that show that the plot is a good fit of the simulated data. F-Stat value indicates the significance of the model occurring not by chance, even though it has a large r2 value. The DX is a measure of the difference in composition value of the rich-solution flowing from the absorber into the generator and the lean-solution stream leaving the generator after rectification back into the absorber. The parameter values, the parity and residual plots for the model (Tables 4 and Figure 8) showed a very close approximation of the fit with the data. Thus the model Equation 14 is a good representation of the simulated data. This concentration gap of the CAHP is akin to the concentration difference between the stream flowing downwards into a plate from an upper plate and that coming out of the plate into a further lower plate of the distillation column. The model equation [DX = f(hA,HA)] Equation 15, has the following regression parameters: the coefficient of determination (r2), of the model is Figure 8(a and b) Parity and Regression Plots for the CAHP [DX = f(H2, H5) Model (a) (b) Figure 9(a and b) Parity and Regression Plots for the Distillation [DX = f(hA, HA) Model

(a) (b) 0.9271 which is a good fit for the data. The fit standard error and the F-Stat value are 0.01686 and 4.0446 respectively, which are good statistical data for the fit as well. The model parameter values and the regression analysis values (Table 4 and Figure 9) also showed that the model is a good fit. Close examination of the models (Equations 14 and 15) also revealed that the two models are of the same Chebyshev model equation type; Chebyshev X,Y Rational Order 5/6 with slightly different parameters. For the fact that the same Chebyshev models could fit the two thermal systems confirms the similarities between the plate-to-plate operation of the distillation and the operation of the CAHP. Based on the similarities of these models, the distillation column which could be viewed as a cascade of several CAHP can thus be analyzed using the COPAHMO as the measure of its stage-to-stage performance. It could then be said that stages where the COPAHMO falls below 1 shall indicate regions of lower energy efficiency and vice-versa. It should be noted also that since COP is a measure of the ratio of heat delivered to work energy consumed, the higher the COP value, the more efficient the work energy was utilized in the process, thus resulting in minimal exergy losses within the stage. Figures 10(a and b) are plots of the distillation COPAHMO at varying feed plate location and feed inlet temperature. For the inlet feed temperature ranging from 302.45K to 352.45K, and the feed plate location ranging from plate 3 to plate 7, it could be seen that the COPAHMO increases with increase in the inlet feed temperature as the feed plate location shift towards plate 3. At each temperature of the feed, plate 3 gives the highest COPAHMO values. COPAHMO is a measure of the ratio of the separating effect (i.e. the energy utilized in effecting separation within the column) to the work energy input into the system to drive/achieve the separation. The higher the COPAHMO value, the better the energy conversion and the lower the energy wastage. +onclusion The COPAHMO model developed could be used to analyze distillation operations, since its been shown that the operation of an absorption heat pump is similar to that of the plate-to-plate distillation operation. Extending the principles of heat engine and heat pump to distillation operation did provide a better understanding to the energy transformation processes within a distillation column, and will thus make its analysis simpler. REFERENCES
1. Adefila, S.S. (1983). Studies on high temperature heat pump. (Unpublished Ph.D. Thesis). University of Salford, United Kingdom. 2. Aspen Technology V11.1, Cambridge, Massachusetts: Aspen Plus. Figure 10(a): COPAHMO of Distillation at Varying Feed Plate Location Figure 10(b): COPAHMO of Distillation at Varying Feed Temperature 3. Bugaje, I. M. (1987). Solar-powered ammonia-water heat pump for refrigeration and airconditioning applications. (Unpublished M.Sc. Thesis). Ahmadu Bello University, Zaria, Nigeria. 4. Cengel, Y.A., Boles, M.A. (2007). "Thermodynamics: An Engineering Approach", sixth ed. McGraw-Hill, New York. 5. Demirel, Y. (2004). Thermodynamic analysis of separation systems. Separation Science and Technology, 39 (16), pp. 3897 3942. 6. Demirel, Y. (2006). Retrofit of distillation columns using thermodynamic analysis. Separation Science and Technology, pp. 1 26.

7. Dhole, V.R., and B. Linnhoff (1993). Distillation column targets. Computer and Chemical Engineering, 17 (5-6), pp. 549 560. 8. Holland, F.A., Pendyala V. R., Devotta S. and Watson, J.A. (1981a). Derived thermodynamic design data for heat pump systems operating on R-C318. Unpublished Technical Memorandum No. 43 of the Heat Pump Research Group of University of Salford, United Kingdom. 9. Ognisty, T.P. (1995). Analyze distillation columns with thermodynamics. Chemical Engineering Progress, 91 (2), pp. 40 46. 10. Olawale, A.S. (2006). Development of generalized Performance Equations for Vapour Compression Heat Pumps. (Unpublished Ph.D. Thesis). Ahmadu Bello University, Zaria, Nigeria. 11. Pinto, F.S., Zemp, R., Jobson, M. and Smith, R. (2011). Thermodynamic Optimization of Distillation Columns. Chemical Engineering Science 66, 2920-2934. doi:10.1016/j.ces.2011.03.022 12. Rashad, A. and A. El Maihy (2009), Energy and Exergy Analysis of a Steam Power Plant in Egypt, Proceedings of 13th International Conference on Aerospace Science and Aviation Technology, ASAT 13, May 26 28. http://www.asat@mtc.edu.ng 13. SYSTAT (2002), TableCurve 3D v4 for Windows Users Manual, SYSTAT Software Inc., USA. 14. U.S. Dept. of Energy, (1984) Assessment of Potential Energy Savings in Fluid Separation Technologies: Technology Review and Recommended Research Areas, Office of Industrial Programs, Washington D.C., Document No. DOE/ID/1247634. 15. Vuckovic, G.D., Vukic, M.V., Stojiljkovic, M.M., and Vuckovic, D.D. (2012). Avoidable and unavoidable exergy destruction and exergo-economic evaluation of the thermal processes in a real industrial plant. Thermal Science: 16 (2), pp. S433-S446. 16. Yuehong B.I, Lingen, C. and Fengrui, S. (2010). Exergetic efficiency optimization for an irreversible heat pump working on reversed Brayton cycle. Journal of Science: 74 (3), pp. 351363. Indian Academy of Science

Table 4: Coefficient values for the DX = f(H2,H5)] Model for CAHP and [DX = f(hA,HA)] Model for Distillation Operation Model Parameter [DX = f(H2,H5)] Model for CAHP [DX = f(hA,HA)] Model for Distillation Value Std Error t-value Value Std Error t-value a -0.77674 1.114368 -0.69703 0.588184 9.792381 0.060066 b -80.2155 675.9666 -0.11867 -7.77366 14.85672 -0.52324 c 78.555 678.5875 0.115763 6.723359 18.782 0.357968 d 43.78763 131.9251 0.331913 -4.67993 84.39004 -0.05546 e -42.4054 134.6821 -0.31486 4.011293 77.08471 0.052037 f 40.50992 114.467 0.353901 3.803114 35.87903 0.105998 g -39.5067 120.5743 -0.32765 -4.398 29.57186 -0.14872 h -30.1011 68.30905 -0.44066 2.467435 42.02385 0.058715 i 29.16088 71.90439 0.405551 -2.73107 48.71316 -0.05606 j -12.1495 136.564 -0.08897 -0.98156 15.41612 -0.06367 k 11.64996 131.1154 0.088853 1.947654 16.70337 0.116602 l 16.97948 44.95445 0.377704 -0.64831 13.81344 -0.04693 m -16.4992 41.31476 -0.39935 1.477748 25.65283 0.057606

n 5.717547 99.89768 0.057234 0.265233 7.25245 0.036572 o -5.47391 97.41082 -0.05619 -0.8297 10.61667 -0.07815 p -4.92046 60.62621 -0.08116 -0.15664 2.768366 -0.05658 q 4.746315 58.28212 0.081437 -0.28398 5.332944 -0.05325 r -1.9869 14.4097 -0.13789 0.036105 1.79994 0.020059 s 1.887808 13.89249 0.135887 0.166828 3.259662 0.051179 t 1.996435 35.81818 0.055738 -0.07489 1.793275 -0.04176 u -1.95081 35.04887 -0.05566 0.023153 0.66025 0.035067 v 1.114084 4.880477 0.228274 0.064858 0.796076 0.081473 aa -1.08455 4.753724 -0.22815 -0.01192 0.556401 -0.02142 P-08 Production of Cellulosic Ethanol from Sawdust modified with Ammonium Sulphate 1Bassey, E. N., 2Oboh, I. O., 2John, A. B. and 2Yesufu, S. O. 1Department of Chemical/Petrochemical Engineering, Akwa Ibom State University, Ikot Akpaden, Nigeria 2Department of Chemical and Petroleum Engineering, University of Uyo, Uyo, Nigeria. Abstract The production of ethanol from a cellulosic material was investigated. The saw dust was hydrolysed to simple sugars and then filtered to separate lignin. The resulting filtrate was neutralized with sodium hydroxide for optimum fermentation to occur. The hydrolysates were fermented in a batch reactor using Saccaromyces cerevisiae and were divided into four samples containing 10g, 20g and 30g of Ammonium sulphate for Sample A, B and C respectively and none for the Control sample. The four samples were monitored over a four day period for parameters such as % yield alcohol, pH, sugar concentration and specific gravity. The results obtained showed that the samples loaded with nutrient gave the greatest rise in % yield alcohol. The Control sample showed only a 35% drop in sugar concentration at the end of the fermentation period. All four samples showed an increase in acidity levels, with the Control sample being the most acidic after four days. Cellulose from sawdust, a by-product of the wood industry, as a source for ethanol production has been shown to be viable considering the level of drop in sugar concentration, pH and specific gravity and the rise in % yield alcohol produced. Keywords: Ethanol, Sawdust, Fermentation, Cellulose, Ammonium sulphate, Nutrient, Saccaromyces cerevisiae. Introduction The recent rise in gas prices, depletion of crude oil reserves, the attendant increase in greenhouse emissions and waste management, have resulted in the need for bio-ethanol production. Wood consists of cellulose (C6H10O5), resins, inorganic salts and water. The quantity of water present has great effect on the heating value and ranges from 25-50% in greenwood and from 1020% air-dried wood (Nabi and Joz, 2001). Sawdust is composed of the particles of wood and is the by-product of sawmills. Chemically, it consists basically of cellulose, hemicelluloses, water and some inorganic salts (Lilbolt et al., 2001). It has a variety of practical uses including serving as a fuel or in the manufacture of particle board. Ethanol is a flammable, colourless, slightly toxic chemical compound with the molecular formula C2H5OH, and is commonly referred to simply as alcohol. Its ease of production with minimum equipment and its low toxicity makes it find application as a solvent for substances intended for human contact, consumption and medicines. It is superior to gasoline because it burns cleanly, almost non-polluting, gives extra power to certain engines and is safe and easy to

handle (Lodgson, 1994). The process of producing ethanol from sugar can prove to be very expensive due to the cost of the feedstock and its wide usage. This in turn affects availability, thus making it more competitive. The choice of raw material is not merely a matter of which one has the greatest yield, but also a question of economics (Mother Earth News, 2006). The use of sawdust will help reduce this competition. Sawdust, being waste, is often disposed of into the environment and thereby becomes a pollutant. The use of sawdust as a feedstock for ethanol production will help reduce the impact of this waste on the environment. The processes of fermentation convert simple sugars to alcohol (Mcgraw Hill, 1982). When certain species of yeast, especially Saccharomyces cerevisiae metabolize sugar in the absence of oxygen, they produce ethanol and carbon dioxide (Opara, 2002). Therefore it is best to agitate the fermenting mash for about 10 minutes to encourage reproduction, and then cover it up, allowing it to stand (Mother Earth News, 1980). Conversion of sugars to alcohol and CO 2 can be completed in 3-5 days depending on the temperature of the mixture and the type of yeast used. The purpose of this study is to know the effect Ammonium sulphate as nutrient for the yeast, will have on the production of ethanol from acid hydrolysed sawdust which is a by-product of wood and a pollutant. Materials and Methods Collection of Sample The sawdust used for this study was collected from a saw mill at the Itam wood market in Uyo LGA in Akwa Ibom State. It was screened to remove impurities and then dried for three days at room temperature. Preparation of Sample Acid hydrolysis of sawdust 400g sawdust sample was put into a vessel and 2.5L concentrated sulfuric acid was added to it. The sample turned black with the evolution of heat. The contents were stirred vigorously with a glass rod for about 10 minutes. Thereafter, the vessel was left for about a day to allow for further reaction. 50ml distilled water was then added to the sawdust-acid mixture. The hydrolyzed sample was then filtered using a filter paper. 3L of a 1M solution of Sodium hydroxide was used to neutralize 200ml of the hydrolysates and this raised the pH of the filtered solution to a range of 4-5 in order to allow for yeast survival. Yeast activation/pitching 10g of Saccharomyces cerevisiae was activated in a sugar solution (containing 20g of sugar and 200ml of warm water at a temperature of 420C). After 20 minutes of activation, the mixture was transferred into four beakers containing the neutralized sample (Maynard, 1970). Fermentation Ammonium sulphate was used as the nutrient and added at various amount as shown below: Sample A contained 10g of Ammonium sulphate; Sample B contained 20g of Ammonium sulphate; Sample C contained 30g of Ammonium sulphate. The Control sample was not loaded with Ammonium sulphate. The jars were sealed with lids to enable the commencement of anaerobic fermentation for the duration of four days. Results and Discussion The fermentation process was monitored on a 24 hour basis and samples were taken for daily analysis of pH, specific gravity, sugar concentration and % yield alcohol by weight and by volume. At the end of the four days fermentation, graphs of sugar concentration, specific gravity

and % alcohol by weight and by volume were each plotted against time in hours. These parameters were determined using the standard Anion Paari Alcolyzer. The percentage alcohol content of all samples was observed to rise with time. The Control sample showed the least increase in % yield alcohol after the four days period. On the first day, samples A, B and C recorded negative values of % yield alcohol which shows that there was no alcohol production, as fermentation had not yet occurred. As fermentation progressed, their % yield alcohol contents increased gradually as shown in Figures 1 and 2. There was no marked increase for the Control sample when compared to that of the loaded samples, indicating that Ammonium sulphate added to samples A, B and C helped boost the yeast performance as higher volume of alcohol was being produced on subjection to similar fermentation conditions. The immediate rise exhibited by the curve could mean increased cell activities. Figure 1: Variation of Alcohol (%w/v) with time.
-1 0 1 2 3 4 5 6 7 012345 Alcohol (% w/v) Time (days) CONTROL A B C

Figure 2: Variation of Alcohol (%v/v) with time. Sugar concentration (0Brix) is a measure of the sugar contained in the media as fermentation progresses. It is also an indication of the degree of fermentation i.e. ability to convert sugar to alcohol. It is observed that for the Control sample, the sugar concentration dropped over the four days time period from 12.78 to 8.25. The loaded samples A, B and C recorded an immediate drop to zero as shown in Figure 3, which indicated a high performance by yeast boosted by the Ammonium sulphate in the fermentation media. The sugar concentration decreased as fermentation progressed showing that the yeast cells were consuming sugar and conversion was taking place. Thus, loading the Samples with nutrient reduced the time it would take the yeast cells to produce a certain volume of alcohol.
-1 0 1 2 3 4 5 6 7 8 9 012345 Alcohol (% v/v) Time (days) CONTROL A B C

Figure 3: Variation of Sugar concentration with time. Figure 4 show that the acidity of all four samples increased generally but within a minutely differential range over the four days of fermentation. The Control sample recorded a steady decline in pH values showing continuously increasing acidity. The loaded samples recorded increase in acidity levels for the first two days whereby their pH values were observed to rise, but still within a high acidity range, thus providing the yeast with a suitably acidic media with which to metabolize the nutrients to produce higher alcohol volumes. Therefore, nutrient loading with ammonium sulphate results in decreased total acidity and increased pH.
-2 0 2 4 6 8 10 12 14 16 012345 0Brix Time (days) CONTROL A B C

Figure 4: Variation of pH with time. The specific gravity of all four samples recorded a marked decrease during the first 24 hours, with that of the Control sample having the least difference as seen in Figure 5. Since specific gravity is the ratio of density of water to that of alcohol, this indicated that there was still more water left in the media with the Control sample, as compared with the loaded samples A, B and C.
3 3.2 3.4 3.6 3.8 4 4.2 4.4 4.6 4.8 5 5.2 012345 pH Time (days) CONTROL A B C

Figure 5: Variation of Specific Gravity with time. Table 1: Ethanol yield from acid-sawdust mixture after fermentation Day Sample A(g/g) Sample B(g/g) Sample C(g/g) Control(g/g) One 0.45 0.45 0.45 0.31 Two 0.39 0.41 0.46 0.28 Three 0.46 0.46 0.39 0.32 Four 0.46 0.46 0.46 0.31

After a 4-day fermentation period, the mean yield of ethanol for the Control sample was 0.31g/g, while the mean ethanol yield for the loaded samples was 0.45g/g as can be calculated from the result data in Table1. This suggests that the greater amount of ethanol is produced in the loaded samples per unit mass of sugar consumed. Therefore, ethanol yield is greater in the samples loaded with ammonium sulphate than the control sample which was not loaded with ammonium sulphate.
0.98 0.99 1 1.01 1.02 1.03 1.04 1.05 1.06 012345 Specific Gravity Time (days) CONTROL A B C

Conclusion Cellulose waste (sawdust) as a strategy for ethanol production via acid hydrolysis has been shown to be efficient considering the rise in % yield alcohol produced and the level of drop in sugar concentration, pH and specific gravity. The yield of ethanol is affected favourably by nutrient loading with ammonium sulpahte. Scale up of this strategy is very promising and should be encouraged. References Lilbolt, L. and Lawther, J. (2001); Nature Organic Fibre in Comprehensive Compositive Material. Elsevier, Amsterdam. pp. 303-325. Lodgson,J. E. (1994). Ethanol in Encyclopedia of Chemical Technology, 4 th Ed. New York: Wiley, p. 817. McGraw Hill Encyclopaedia, (1982); Kinetic Synthesis on Fermentation. 2nd Edition, McGraw Hill companies, New York. Pp. 1314-1346. Mother earth News, (1980); Journal on Alcohol Fuel. http://motherearthnews.com Nabi, S. D. and Joz, J. P. (2001). Natural fibre polymer composite. A review advances in polymer Technology, 18(a) 35-363. Opara, C.C., (2002); Biochemical and Microbiological Engineering.1st Edition, Academic press. Pp 87-91. P-09 REVIEW OF SAWDUST PRETREATMENT PROCESSES FOR BIOFUEL PRODUCTION Kuye Ayoade, Onuora Okorie and Edem Utibe Benedict Department of Chemical Engineering, Faculty of Process Engineering, University of Port Harcourt, Choba, Rivers State. E-mail: ayokuye@yahoo.com Abstract Development of sustainable energy systems based on renewable sawdust feedstock is now a global effort. Sawdust contains polymer of cellulose, hemicellulose, and lignin bound together in a complex structure. Bio-fuel products can be obtained from sawdust through several biochemical and thermochemical conversion processes. From a biochemical

viewpoint, since the cellulose component of the sawdust is recalcitrant to biodegradation the sawdust is subjected to an initial pretreatment step in order to become liable to biochemical conversion. The technology of converting sawdust feedstock into bio-fuel can also be achieved through a combined use of heat and chemical catalyst often referred to as thermochemical conversion processing. This is an attractive option due to its higher efficiencies and greater versatility. But the 30-60wt. % moisture content of raw sawdust feedstock coupled with problems of size specification often results in poor or unacceptable values in various properties of the bio-fuel product. To pacify these problems, the sawdust feedstock is also subjected ab initio to a variety of thermochemical pretreatment processes. Pretreatment processes are therefore crucial for obtaining bio-fuel products from sawdust. This paper reviewed the various available pretreatment methods used for converting sawdust to bio-fuel products. Key words: Sawdust, lignocellulosic material, pretreatment, hydrolysis. 1. Introduction With the rapid development of the global economy, energy requirements have increased remarkably, especially in emergent countries. The realization that fossil fuel resources required for the generation of energy are becoming scarce and that climate change is related to carbon emissions into the atmosphere has increased interest in the development of ecofriendly renewable energy sources such as wood sawdust. Wood sawdust is an organic matter available on a renewable and sustainable resource with great potential as an alternative to fossil fuels for supplying energy (Kumar et al., 2009). It is generated by mill processing of wood timbers obtained from forest all over the country. It is composed of three major components namely; cellulose (a polymer of glucosan), hemicelluloses (also called polyose), and lignin (a multi-ring organic compound) in addition to minor quantities of compounds such as lipids, proteins, simple sugar, starches, water, hydrocarbons and ash (Sun and Cheng, 2002; Dagnino et al., 2013). Consequently, it is often referred to as a ligno-cellulose substance to reflect its two defining constituents: lignin and cellulose respectively. However, the cellulose is recalcitrant to biodegradation and needs to be hydrolyzed in an initial pretreatment step into its constituent cellobiose units and into simpler D-glucose units in order to be liable to biochemical conversion processes such as esterification, fermentation or anaerobic digestion. The rate and extent to which cellulose in sawdust can be enzymatically hydrolyzed is limited by two important factors: the close physical and chemical association between lignin and the cell wall polysaccharides, and the degree of crystallinity within the cellulose polymer itself. Hence, to hydrolyze wood sawdust with enzymes successfully, it is important to apply a suitable pretreatment that can effectively disrupt linked lignin and crystalline cellulose. This in turn opens up its lignocellulosic structure which further increases its accessible surface area thus exposing the cellulose constituent to enzymatic attack (Dagnino et al., 2013). In addition, it reduces the cellulose crystallinity while increasing its porosity, pore size, and pore volume (Dagnino et al., 2013; Sun and Cheng, 2002; Mosier et al., 2005) for further enzyme penetration. The technology of converting sawdust feedstock into bio-fuel can also be achieved through a combined use of heat and chemical catalyst often referred to as thermochemical conversion processing. This is an attractive option due to its higher efficiencies and greater versatility. It includes processes such as pyrolysis, gasification and combustion. But the 30-60wt. %

moisture content of raw sawdust feedstock coupled with problems of size specification often results in poor or unacceptable values in various properties of the bio fuel product. To pacify these problems the sawdust feedstock is also subjected ab initio to a variety of thermochemical pretreatment processes depending on the nature and state of the sawdust feedstock. Although, several recent review articles provide a general overview in the field of lignocelluloses substance pretreatment (Ayeni et al.,2013; Carvalheiro et al., 2008; Hendriks and Zeeman, 2008; Mtui, 2009; Agbor et al., 2011; Wyman et al., 2005; Mosier et al., 2005), most of the pretreatment methods they proposed have failed to meet the basic requirements for efficient sawdust pretreatment. 2. Efficacy of pretreatment Many pretreatment methods applicable to sawdust have been studied, and are still in development. It is difficult to evaluate and compare pretreatment technologies because they involve processing cost, capital investment, and chemical recycling (Jeoh et al., 2007). However, mass balance analysis can be used to validate the pretreatment efficacy of a process with any given feedstock. This necessitates thorough economic analysis to determine the best pretreatment method suitable for a particular local feedstock. Ultimately, the chosen pretreatment process should have a low capital and operational cost. The pretreatment technology for converting sawdust feedstock into bio-fuel product can be broadly classified under biochemical, mechanical or thermochemical processing. Each of them encompasses several pretreatment methods. Fig. 1 situates these pretreatment methods in a summarized bio-fuel conversion routes diagram. A literature survey on these pretreatment methods as it applies to sawdust is conducted in the next section. Fig. 1: Modified summary of bio-fuel conversion routes (Chen et al., 2011; Chew and Doshi, 2011). 3. Biochemical Pretreatment Methods Biochemical pretreatments have been mostly been associated with the action of enzymeproducing fungi and chemicals that can degrade or effectively disrupt linked lignin and crystalline cellulose of the sawdust feedstock. The biochemical pretreatment methods reviewed in this section include: acid hydrolysis, alkaline wet oxidation, ammonia fiber expansion, ozonolysis, and steam expansion/hydrothermal. 3.1 Acid Hydrolysis Acid hydrolysis is the most commonly adopted technique (Badger et al., 2002). It is an effective method used for lignocelluloses raw material pretreatment in saccharification which could change into ethanol. Although acids are powerful agents used for biomass hydrolysis, concentrated acids are toxic, erosive and hazardous. Handling higher concentrations of acid requires reactors that are resistant to erosion in raw material pretreatment. Diluted acid hydrolysis especially sulfuric acid has been successfully developed for pretreatment of cellulosic materials (Kumar et al., 2011). Kim (2005) conducted a two-stage dilute-acid catalzed hydolysis pretreatment procedure on hemlock sawdust aiming to recover hemicellulose and cellulose at different stages. In the first stage, sawdust was hydrolyzed at 190 C for 150 s with 1.1wt% sulfuric acid and 46.0 wt% total solids. As a result, 69.3% mannose, 74.2% galactose, 67.7% xylose, and 17.4% glucose

of their theoretical maximum yields were achieved, which reveals that hemicellulose was the major target in the first-stage hydrolysis. After recovering soluble sugars by washing from the first-stage hydrolysate with water, the washed first-stage hydrolysate solids were hydrolyzed again in the second stage at more severe conditions, such as 2.6 or 3.5 wt% H2SO4, 205 or 210C, and 80135s. After the two stages, the highest overall yields from 100 g of dry hemlock sawdust were a total of 39.3 g of fermentable sugars (36.0 and 3.3 g of hexose and pentose sugars, respectively). These results indicate that hemlock sawdust could be used to produce fermentable sugars which can be converted into other value-added bio-based products. Yang and Wyman (2009) reported that the use of dilute sulfuric acid in the pretreatment operation can increase recovery of hemicellulose sugars substantially to about 85-95% of the maximum possible versus only about 65% if no acid was employed. Alhasan et al. (2010) studied the combinatorial nitric acid and sodium hydroxide pretreatment for improving the enzymatic saccharification of rubber wood sawdust. They reported that the enzymatic hydrolysis experiments showed that a glucose yield of 95% was achieved (within 24 h of hydrolysis) with rubber wood sawdust sample pretreated using 6% HNO3, at 100C for 60 min followed by 1%NaOH at 90C for 30 min. They also compared their results with those reported in literature and found that combining nitric acid and sodium hydroxide pretreatments resulted in higher rate of hydrolysis and better cellulose digestibility. Kumar et al. (2011) studied the hydrolysis of wood sawdust by combined chemical pretreatment and enzymatic methods for lignocellulosic saccharification. They found that the treatment with 1N H2SO4 after Aspergillus fumigatus extracellular enzymatic hydrolysis gave higher value of the reducing sugars (0.990.001g/l). Kim et al. (2013) studied ethanol production from poplar sawdust using sulphuric acidassisted continuous twin screw-driven reactor (CTSR) pretreatment followed by simultaneous saccharification and fermentation (SSF). They reported that pretreatment with high acid concentration increased the cellulose content in the pretreated solid (74.9-76.9% in the range of 4.0-5.5wt.% H2SO4). They also reported that the XMG (xylan + mannan + galactan) recovery yield of the sample treated with 4wt. % H2SO4 at 185 was maximized at 88.6%. 3.2 Alkaline Wet Oxidation Ayeni et al. (2013) studied alkaline wet air oxidation (WAO), alkaline peroxide assisted wet air oxidation (APAWAO) and enzymatic hydrolysis for conversion of shea tree sawdust to reducing sugars. They found that the yield of reducing sugars from WAO optimized conditions by two enzyme preparations (cellulose and glucosidase) was 131mgg-1 of dry substrate while the APAWAO yielded 274mgg-1. They also reported that these pretreatments used showed to have a disrupting effect on the sawdust, making the treated materials accessible for enzymatic hydrolysis. 3.3 Steam Explosion and Ammonia Fiber Explosion (AFEX) Steam explosion (autohydrolysis) is the most commonly used method for pretreatment of lignocellulosic materials (McMillan, 1994; Sun and Cheng, 2002). In this method, chipped sawdust is treated with high-pressure saturated steam and then the pressure is swiftly reduced, which makes the materials undergo an explosive decompression. Ammonia fiber explosion (AFEX) is another bio-chemical pretreatment process in which sawdust is exposed to liquid ammonia at high temperature and pressure for a period of time,

and then the pressure is suddenly reduced. The AFEX process is very similar to steam explosion (Sun and Cheng, 2002). It has been reported that AFEX has been applied successfully to herbaceous and agricultural residues (Holtzapple et al., 1991) with approx. 100% of the theoretical glucose yield, but it only works moderately well on hardwoods and not attractive for softwood derived materials (Holtzapple et al., 1991; Ogier et al., 1999; Mosier et al., 2005). Ojumu and Ogunkunle (2005) investigated the production of glucose in batch reactors from hydrolysis of lignocelluloses under extremely low acid (ELA) and high temperature condition. In the course of their investigation, sawdust was pretreated by auto-hydrolysis ab initio. They reported that the maximum glucose yield obtained was 70% for the pretreated sawdust at 210oC in the 18th minute of the experiment and this value was 1.4 times the maximum glucose obtained from the untreated sawdust under the same condition. 3.4 Ozonolysis In this process, ozone is used to change the structure of lignocellulosic materials. Ozonolysis is carried out at room temperature and normal pressure. It can effectively remove the lignin without producing any toxic residues. The main restriction of this process is the large amount of ozone utilization that makes the process expensive (Sun and Cheng, 2002). Vidal and Molinier, (1988) reported that enzymatic hydrolysis yield increased from 0% to 57% as the percentage of lignin decreased from 29% to 8% after the ozonolysis of pre-treatment of poplar sawdust. 4. Theromchemical Pretreatment Methods The technology of converting sawdust feedstock into bio fuel can also achieved through a combined use of heat and chemical catalyst often referred to as thermochemical conversion processing. This section review of some of the pretreatment methods applied to sawdust feedstock before their thermochemical conversion. 4.1 Fast Pyrolysis Fast pyrolysis is a thermal process which involves the rapid heating of organic material to a high temperature in the absence of an oxidizing agent (air or oxygen), which then vaporizes and condenses to bio-oil (Bridgwater and Peacocke, 2000; Mohan et al., 2006; Zhang et al., 2006; Lede et al., 2007; Van de Velden et al., 2010;; Jendoubi et al., 2011). Other products of fast pyrolysis include the solid char and non-condensable gases. There are four essential/key features of a fast pyrolysis process (Bridgwater and Peacocke, 2000; Bridgwater, 2003, 2012): (1) Very high heating and heat transfer rates of >1000 are used, which usually requires a finely grounded sawdust feed. (2) Carefully controlled pyrolysis reaction temperature of about 500 and vapour phase temperature of 400-450 (Salehi et al., 2009). (3) Short vapor residence times are used (typically <2s) (Isahak et al., 2012; Bahng et al., 2009; Van de Velden et al., 2010; Butler et al., 2011). (4) Pyrolysis vapors and aerosols are rapidly quenched or cooled to freeze the pyrolytic products and to avoid secondary cracking (Kang et al., 2006; DeSisto et al., 2010; Demirbas and Arin, 2002). Compared with other available conversion technologies, fast pyrolysis is the least developed and most promising for converting sawdust to liquid fuels and also for industrial implementation (Park et al., 2008a; Bridgwater et al., 2002; Jendoubi et al., 2011; Jung et al., 2008). Typically, fast pyrolysis processes produces 50-75wt. % of liquid bio-oil,

15-25wt. % of solid char, and 10-20wt. % of non-condensable gases [Mohan et al., 2006; Bridgwater, 2003, 2004; Jendoubi et al., 2011], and the water content in bio-oil is usually limited to about 15-35wt. % (Mohan et al., 2006; Yaman, 2004). No waste is generated because the bio-oil and solid char can each be used as a fuel and the non-condensable gases can be recycled into the pyrolysis process (Mohan et al., 2006). Jung et al. (2008) studied the fast pyrolysis of bamboo sawdust and rice straw using a bubbling fluidized bed reactor. They reported that the maximum bio-oil yield with respect to bamboo sawdust was 70wt. % and the optimum reaction temperature for the production of bio-oil was between 405-450 using a product gas as fluidizing medium, particle size of 0.60.85mm and flow rate of 2.1-3. Park et al. (2008a) studied the fast pyrolysis of Japanese larch sawdust in a bubbling fluidized bed reactor and reported that the maximum bio-oil yield was 64% at pyrolysis temperature of 400-550 with particle size between 0.3-1.0mm. Heating rate of 5-20 and superficial velocity of 0.7-1.3cm/s was used. Similarly, Park et al. (2008b) obtained a bio-oil yield 50% (by mass) from fast pyrolysis of radiata pine sawdust at 400-450C in a bubbling fluidized bed reactor. Oasmaa et al. (2010) studied the fast pyrolysis bio-oil from pine wood sawdust (pinus sylvestris) and agricultural residues using a transport bed reactor. They reported that the typical bio-oil yield from pine wood sawdust was 64wt. %. DeSisto et al. (2010) studied the fast pyrolysis of pine sawdust (40 mesh) in a fluidized-bed reactor; they reported that the average bio-oil yield from the runs (40, 41 and 52) was approximately 65%. Heo et al. (2010) carried out analysis on waste furniture sawdust via fast pyrolysis in a fluidized bed reactor. They reported that the maximum bio-oil yield was 57.0% at pyrolysis temperature of400-550. The particle sizes used was 0.3-1.3mm and gas flow rate of 3-5/Lmin. 4.2 Drying Drying is a major step in the pretreatment of sawdust. Raw sawdust feedstock needs to be dried to bring down the moisture from 30-60wt. % to below 10wt. % -although up to 15wt. % can be acceptable (Fagernas et al., 2010)- thus avoiding adverse effects of water on stability, viscosity, pH, corrosiveness and other liquid properties in the pyrolysis product. Usually, sawdust drying is carried out mainly to increase sawdust energy input and minimize the risk of microbial decomposition. The drying process sometimes can be problematic due to sizing specifications and poor sawdust grindability. Wang et al. (2008) studied the influence of microwave drying on pine wood sawdust pyrolysis. A microwave oven (MO) was used to dry the sawdust using four power levels i.e. 200, 400, 600 and 800W. They reported that the moisture removal property was highly dependent on the power capacity. The bio-oil yield obtained using microwave oven (MO) and electrical oven (EO) drying were 69.87% and 67.37% respectively. Under optimized condition, a much shorter dehydration time was achieved with MO (6mins at 600W) compared to EO drying (~40mins). 4.3 Torrefaction In recent decade, a pre-treatment technique known as torrefaction proposed for thermal conversion process has showed positive results. Torrefaction is a thermolysis process that subjects the sawdust feedstock to thermal treatment at relatively low temperatures of 200300 in the absence of oxygen. Definition for torrefaction is commonly associated with roasting,

mild pyrolysis, slow pyrolysis, and thermal pretreatment, according to its utilization. Early research work on torrefaction was mainly on wood based material such as woodchips and sawdust (Uslu et al., 2008). In the recent years, more studies incorporate agricultural crops and agro-forestry residue. Torrefied biomass typically contains 70% of its initial weight and 90% of the original energy content (Bergman, 2005). The moisture uptake of torrefied biomass is very limited, varying from 1% to 6 % (Uslu et al., 2008). Even though torrefaction is in its infancy, several studies show that is highly efficient for thermochemical processing (Uslu et al., 2008). It increases the energy density, hydrophobic nature and grindability properties of biomass (Bergman, 2005). Recent studies by Tumuluru et al. (2011; 2012) on pretreatment methods for bioenergy applications, indicates that torrefied material makes a good fuel for biofuels applications, such as co-firing. In addition, they reported that torrefaction of biomass not only increases biomass energy properties, but produces some higher hydrocarbons as well, which can typically be used for producing chemicals or for improving overall energy efficiency. Pimchuai et al. (2010) reported a study on torrefaction of sawdust, rice husks, peanut husks, bagasse and water hyacinth under various temperature and residence time of 250, 270, and 300C and 1, 1.5 and 2 hours respectively. The study reported an increase in the calorific value of the torrefied product; a decrease in the percentage of mass and energy yield; as well as a decrease in the moisture and volatile matter contents with increasing temperature and residence time. The findings also revealed that temperature has more effects on torrefaction than the residence time. Chew and Doshi (2011) did a review of various studies on torrefaction. The review aims at comparing and compiling the various works on torrefaction on different biomass- sawdust inclusive. It examined their physical and chemical properties before and after torrefaction. The physical and chemical properties analyzed include: yield, energy content, elemental composition, change in major components and hydrophobicity. The results obtained demonstrate a net increase in heating value of about 18-26MJ/kg for all woody biomass. The elemental analysis showed an increase in fixed carbon content as torrrefaction conditions intensified. The higher loss in oxygen and hydrogen compared to carbon was attributed to the increase in energy value of the biomass. Overall the results of the study showed an improved property values in hydrophobicity, friability and energy content of the torrefied biomass. Excerpts of their results are shown in Tables 1 and 2. Table 1: Ultimate analysis, proximate analysis and higher heating value (HHV) of sawdust (modified from Chew and Doshi, 2011). Biomass Ultimate analysis (wt.%) Proximate analysis (wt.%) Higher Heating Value (MJ/kg) CHNO Volatile Matter Fixed Carbon Ash Sawdust 40.85 6.17 0.03 3 9 . 0 7 73.15 13.02 0.38 -

Table 2: Ultimate analysis, proximate analysis and higher heating value (HHV) of sawdust after torrrefaction for torrefaction duration of 0.5h (modified from Chew and Doshi, 2011). Biomass Ultimate analysis (wt.%) Proximate analysis (wt. %) Higher heating value (MJ/kg) CHNO Volatile Matter Fixed Carbon Ash 19.55 Sawdust 45.92 5.20 0.53 37.01 69.10 19.84 8.62 Chiang et al. (2012) investigated the characteristics of 26 varieties of biomass produced from forestry, agriculture, municipality, and industry in Taiwan to test their applicability in thermal conversion technologies and evaluation of enhanced energy efficiency. 4.4 Pelletisation Pelletisation can be defined as drying and pressing of biomass under high pressure to produce cylindrical pieces of compressed and extruded biomass. Pellets have a smaller volume and a higher volumetric energy density compared to wood chips and is hence more efficient to store, ship and convert into energy. The production of pellets requires small feedstock particles, maximum 320mm and moisture content below 1015%. However, piston press pelletisation can handle up to 20% moisture content (Malisius et al., 2000; Stahi et al., 2004). Pelletisation is performed at a temperature of around 150oC. Water plays an important role in densification. If the feedstock is either too dry or too wet, the pressure required for densification increases dramatically. In fact, moisture content of 1025% is considered optimal (Uslu et al., 2008). Thus, the feedstock is heated to 50100oC to soften the lignin and obtain the desired moisture content and at approximately 150oC mechanical densification is applied. The produced pellets have a net calorific heating value in the range of 1618 MJ/kg. The actual value largely depends on the moisture content which varies between 5% and 10% as shown in Table 3. Table 3: Characteristics of wood pellets (sawdust, Cutter Shavings, and Wood-grinding dust as raw materials) [Uslu et al., 2008; Alakangas and Paju, 2002]. 5. Conclusion The pretreatment of sawdust has the potential to contribute to the world energy demand. In recent years, pretreatment studies on various types of sawdust feedstock have shown promising results in the associated bio fuel properties. This paper reviews several of these pretreatment methods. From this review, it is evident that there is a wide range of different VARIABLES Unit Values

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O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+

P-10 A NEW EXPLICIT MODEL FOR PREDICTING FRICTION FACTOR IN A FULLY DEVELOPED TURBULENT PIPE FLOW
Offor, U.H.1 and Alabi, S.B.2 Department of Chemical and Petroleum Engineering, Faculty of Engineering, University of Uyo, Main Campus, Nwaniba Road, Uyo, Akwa Ibom State, Nigeria 1: hconfidence@yahoo.com; 2: sundayalabi@uniuyo.edu.ng ABSTRACT Friction factor estimation cuts across various engineering disciplines. Over the years, Colebrook equation has earned a reputation for estimating friction factor f for fluid flow in pipes due to its theoretical basis. This equation however, suffers from being implicit in f and requires iterative solutions to achieve convergence. This may cause problem in the simulation of flows in a network of piping systems, as it may be necessary to evaluate friction factor many times. Thus, an accurate explicit model is desirable to simplify piping systems design computations and flow simulations. In this paper, a non-linear multivariable regression model was developed for predicting friction factor explicitly, in contrast to the implicit Colebrook equation. Using the f data generated from the implicit Colebrook equation for Reynolds number (Re) and relative roughness in the ranges of 4000 - 108 and 0 0.05, respectively, as a benchmark, the effectiveness of the new model was compared with those of the existing explicit models. The new model gave rise to the least mean square error of 1.6841388 x 10-04.

It is concluded that the new explicit friction factor model is superior to the existing explicit models and can successfully be used in place of the implicit Colebrooks equation for pipe flow calculations. Keywords: Colebrook equation; friction factor; pipe flow; explicit model 1.0 INTRODUCTION Fluid flow in pipes is usually accompanied by a loss of head due to hydraulic resistance between the fluid and the pipe wall (inner surface). The DarcyWeisbach relation (Moody, 1944) given in Eqn. (1) is used for predicting the head loss.

i_ = _
_ __ _

(1) In the laminar regime (Re j %1$$), f is a function of Re only and can be estimated by the equation due to Hagen- Poiseuille (equation (2))

_=
_

__

(2) In the turbulent regime ( & 3 1$_ j __ j 1$_), f is a function of Re and (k/D) and is estimated by the Colebrook and White equation, which is discussed further in section 2.
O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+

2. COLEBROOK EQUATION The Colebrook equation is a combination of the Prandtl smooth-pipe equation given by equation (3) and the von Karman rough-pipe equation given by equation (4) (Moody, 1944).
_ __

= V%log_ !
___ _ __

_-Z_

[ = %log_ 7____\ V $-) (3) = 1-"& + %log_ l _,F (4)

+

BrkiI (2011) noted that, Colebrook equation is known elsewhere as Colebrook White equation. White was not actually a co-author of the paper in which this equation was presented. However, in this paper, Colebrook and Colebrook-White are used interchangeably. The combination of equations (3) and (4) with the data gathered from commercial pipes resulted in the well acclaimed Colebrook model given by equation (5) which is valid for Re and (J/D) in the ranges of & 3 1$_ j __ j 1$_ -E$ $ j l, +F j $-$#, respectively.
_ __

= V%log_ !

_-%_-_ *&__

_-Z_

[ (5)
Equation (5) estimates the DarcyWeisbach friction factor f for fluid flow in pipes. This equation however, suffers from being implicit in f and requires iterative solutions to achieve convergence. The implicit equation can be solved using an electronic spread sheet. However, numerical simulations of pipe pressure drop require computation of friction factor at each grid point and for each time step (Clamond, 2009). This may cause problem in the simulation of flows in a network of piping systems, as it may be necessary to evaluate friction factor many times. Thus, an accurate explicit model is to simplify piping systems design computations and flow simulations. Moody (1944) presented a graphical solution of the Colebrook equation in the Moody chart for estimating f, employing equations (2) and (5) covering for the laminar and turbulent Re ranges, respectively. This eliminates the need for iterations, but the f values may not be accurately read. Moreover, most of the f predictions are done with computers and the need still arises for an approach which can automatically and explicitly generate f values. The quest for a fast, non iterative and accurate model in lieu of the implicit Colebrook equation has given rise to various explicit forms of the Colebrook equation, some of which are described briefly in section 3. 3. REVIEW OF THE EXPLICIT FORMS OF COLEBROOK AND WHITE EQUATION i. Moody (1947) proposed the following model which is valid for Re and (J/D) in the ranges of & 3 1$_ j __ j 1$_ -E$ $ j l, +F j $-$1 respectively.

_ = $-$$## #1 + l% 3 1$_ , ++ _' _F

_ "_

) (6)
O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+ ii. Swamee and Jain (1976) proposed the following model for turbulent flow which is

valid for Re and (J/D) in the ranges of 5000 K Re K 108 and 1$(_ j l, _F j $-$# respectively.
_ __

= V%log_ l _-%_-+ + Z-%_ _H-hF (7)

_ __

iii. Churchill (1973) proposed the following model for turbulent flow

= V%- log_ !
, "+ _-%_ _F -U

+l

[ (8)
He later (1977) proposed the following model valid for all fluid flow regimes (laminar, transition and turbulent regimes) and (J/D) in the range $ j l, +F j $-$#

_ = ) !l _F
__

+ =P + _`(_ "_[
_ "__

(9) Where A = >V%log #l

, "+ _-% _F -U __

F+l

)@
, @ = l_%Z_
_F __

This equation combines the Hagen-Poiseuille equation for the laminar regime, Colebrook equation for the turbulent flow regime and _ = " 3 1$(_ ___ for the transition regime (2100< Re < 4000). This correlation for the transition regime was developed using f values obtained by Wilson and Azad (Churchill, 1977) for smooth pipe for Reynolds number in the range of 1$$$ U __ U #$$$$$ . However, in the transition regime, fluids can exhibit either laminar or turbulent behaviour and are considered unstable. Thus, the friction factor can be difficult to accurately predict at the transition regime. iv. Chen (1979) proposed the following approximation which is valid for Re and (J/D) in the ranges of 4000 j Re j 4 x108 and 1$(% j l, +F j $-$# respectively. This equation involves two internal iterations of the Colebrook equation.
_ __

= V%log_ # , _-% _Z-+ V Z- _Z_

- log_ ! _-__Z% - l, +F
_ _-_ U_

Z-_Z _

_H-:h:A[)

(10) v. Zigrang and Sylvester (1982) proposed the following model which contains three internal iterations of the Colebrook equation
_ __

= V%log_ # _-%-_ V Z- _ _ - log_ ! , _-%-_ V Z- _ _ - log_ l , _-%-_ + __ _F[) (11)

O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+ vi. Serghides (1984) proposed the following approximation. This equation is valid for Re

and (J/D) in the ranges of Re m %1$$ and $ j l, +F j $-$# respectively.

_ = l5_ V
,<(_-,_M,A

=,_(,A`_

F
(_

(12)
where N_ = V%- log_ l ,
_-%_ _

__ ,

F, N_ = V%log_ l _-%_ + _-Z_-2A

_

F, N_ = V%log_ l _-%_ + _-Z_-2_

_

F
vii. Using signomial terms, Manadilli (1997) proposed the following approximation which

is valid for Re and (J/D) in the ranges #%*# j __ j 1$_ and $ j l, +F j $-$#, respectively.
_ __

= V%1?O !
4 5

+ UZ _H-h:< V U_-__ _ [ (13)

_-%

viii. Ghanbari et al (2011) proposed the following approximation which is valid for Re and (J/D) in the ranges %1$$ j __ j 1$_ and 1$(_ j l,
_F

j $-$#, respectively. This model was obtained using f obtained by digitizing the Moody chart.

_ = >V1-#%1?O #!
4 5

%-__[ _- __

+ l_-%__ _F
-U_Z_

)@
(_-__U

(14)
It is not obvious how data was obtained for the Reynolds number between 2100-3000 since the moody chart does not contain data in this range for which their model was validated. ix. Romeo et al (2002) proposed the following approximation which is valid for Re and (J/D) in the ranges of *$$$ j __ j 1-# 3 1$_ and 1$(_ j l,
_F _

j $-$# respectively. = V%-$log6 V Z- _%_ C

_-Z_%

__ = B "+

_-% _Z

*& log B "+ _-__% *& log B "+

#l

%-%U_n_F -UU__

+l

Z-____

_ _-__ZM*&F -U__Z

) Y (15 4. THE PROPOSED NONLINEAR MODEL The following steps were followed to arrive at the nonlinear model presented in this paper. i. The Colebrook model, as given by equation (5) is re-written as

O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+
_ __

= V%log_ # _-%_-_ + _-Z_ *& ! _

__

[) (16)
ii. The _
__

on the right hand side of equation (16) is replaced with the model of the form given by equation (17), similar to that of Ghanbari et al (2011)
_ __

= -1?O !l
, "_ o 8

F
p

+l _F
_

(17) The proposed new model is thus obtained as,

_ __

= V%log_ C _-%_-_ + _-Z_ *& #V-log !l

, "_ o 8

F
p

+l _F
_

[)

(18) iii. Friction factor ( f ) data were obtained from equation (5) for Re values in the ranges of & 3 1$_ j __ j 1$_ corresponding to each (J/D) value ranging from 0 to 0.05 using 28 intervals. iv. Using MATLAB-based surface-fitting tools, coefficients a, b, c, d and e with their parameter bounds were obtained at 95% confidence level (Table 1). The uncertainties associated with the estimated parameters are a measure of the reliability of the parameters, and consequently, a measure of the adequacy of the model. A model whose parameter estimates have narrow intervals (low uncertainties) is deemed to be

good and adequate (Motulsky and Christopoulos, 2003). Table 1. Parameters of the new model
Parameter 8alue Parameter ound 'bsolute relative un"ertainty$3% > F1-))& (-1.885, -1.884) 0.05305 @ *-)%" (3.825, 3.829) 0.05223 + 1-$#) (1.058, 1.059) 0.09442 0 '-&#* (6.452, 6.454) 0.01549 : $-(&#" (0.9455, 0.9459) 0.02114 5. DISCUSSION OF RESULTS A comparison of the new model (equation 18) with some of the existing forms of the implicit Colebrook equation reported in section 3 was done by utilizing the following performance indices.

1. Sum of squared error (SSE) = =_9q__ V __n9abc9_p`_ 2. Mean square error (MSE) =
rLno=_efgh(_hieLDlehm`_
LnA

p _ p

3. Mean absolute relative error (MARE) =

s_efgh( _hieLDlehms _efgh arp ar_

O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+

The SSE is a measure of the discrepancy between the true data and an estimation model. A small SSE value indicates a tight fit of the model to the data and usually equal to zero for a perfect fit. The MARE is a measure how close the predictions are to the actual values. They are both pointers to the accuracy of a model. The MSE gives a distribution of error per data points considered. The results of the comparisons are reported in Table 2. Table 2. Comparison of the explicit equations with the implicit Colebrook equation S/N Equation SSE MSE MARE 1 The new model 1.2058434E-06 1.2397810E-10 1.6841388E-04 2 Romeo et al (2002) 4.9339715E-06 5.0490907E-10 6.0159698E-04 3 Serghides (1984) 9.1941593E-06 9.4086772E-10 5.3804421E-04 4 Zigrang and Sylvester (1982) 9.7794190E-06 1.0007592E-09 6.7550555E-04 5 Churchill (1973) 1.1714613E-03 1.1987930E-07 5.5037998E-03 6 Ghanbari et al (2011) 2.2710925E-03 2.32240816E-07 8.1783726E-03 The performance of the new model is compared with those of the existing models listed in Table 2 with particular reference to equations of Romeo et al (2002), Seghides (1984), and Zigrang and Sylvester (1982) which are ranked best based on their accuracies in the ranges covered by the Colebrook equation. From Table 2, it is observed that the new model has the least SSE and MARE values which are ~76% and ~72% lower than the corresponding SSE and MARE reported for the model developed by Romeo and Co-workers (2002) which ranks next in this report. This indicates that the new model deviates least from the true f values

when juxtaposed with the other models in Table 2. Therefore the new model is more accurate than the existing explicit models. In addition to the high accuracy of the new model, its parameters are observed to have very low uncertainties (j 0.09%) (Table 1). This indicates that the parameters are known precisely and hence very reliable. Consequently, the model is deemed very adequate for predicting friction factor. 6.0 CONCLUSION A new explicit model is developed for friction factor estimation. The model has the least SSE and MARE values of 1.2058434 x 10-06 and 1.6841388 x 10-04, respectively when compared with those of the five (5) literature explicit models. Moreover, the maximum uncertainty associated with the new models parameters is very low (0.09%) which indicates that the parameters are known precisely. It is concluded that for pipe flow design and simulations, the new explicit friction factor model can reliably be used in lieu of the implicit Colebrooks equation to provide accurate estimates of friction factor in the ranges 4000 j Re j 4 x108 (fully developed turbulent flow) and $ j l, +F j $-$#.
O))or an# Ala(i, A new explicit friction factor mo el, !SC"# A$%&Conference, '(o )*1+

Nomenclature hL Head lost due to friction [m] f Darcy friction factor (dimensionless) L Length of pipe [m] D Internal pipe diameter [m] v velocity of flow [m/s] g Acceleration due to gravity [m/s2] k Pipe roughness [m] Re Reynolds number (dimensionless) a, b,c,d,e The new model parameters (Eqn. 18) REFERENCES Allen, J.J., Shockling, M.A., Kunkel, G.J. and Smits, A.J.,(2007). Turbulent flows in Smooth and rough pipes. Phil. Trans. R. Soc. A 15 vol. 365 no. 1852, 699-714 Allen, R. G., (1996). Relating the Hazen-Williams and Darcy-Weisbach Friction loss equation for pressurized irrigation. ASME Vol. 12(6): 685- 693. BrkiI, D., (2011). Review of explicit approximation to the Colebrook relation for flow friction. Elsevier Journal of Pet. Science and Engineering 77, 34-48. Churchill, S. W., (1977). Friction factor equations spans all fluid-flow regimes, Chem. Eng. 84 (24) 91. Clamond, D., (2009). Efficient resolution of the Colebrook equation. Ind. Eng. Chem. Res. 48, 3665-3671. Colebrook,C.F., White, C.M., (1937). Experiments with Fluid Friction in Roughened Pipes. Proc. R. Soc. Lond. A. Math. Phys. Sci., 161, 367-381. Fang, X., Xu,Y., Zhou, Z., (2011). New correlations of single-phase friction factor for turbulent pipe flow and evaluation of existing single-phase friction factor correlations. Nuclear Eng. And Design, 241, 897-902.

Ghanbari, A., Farshad, F., Rieke, H. H., (2011). Newly developed friction factor correlation for pipe flow and flow assurance. J. of Chem. Eng. And Mat. Sc. Vol 2(6), 83-86. Moody, L.F., (1944). Friction factors for pipe flow. Trans AMSE, 66 , 671-681. Motulsky, H.J. and Christopoulos, A., (2003) Fitting models to biological data using linear and nonlinear regression. A practical guide to curve fitting., San Diego CA: GraphPad Software Inc. Romeo, E., Royo, C., Monzon, A., (2002). Improved explicit equation for estimation of the friction factor in rough and smooth pipes. Chem. Eng. J. 86 (369-374) Yildirim, G., (2009). Computer based analysis of explicit approximations to the implicit Colebrook White equations in turbulent flow friction calculation. Adv. Eng Software 40, 1183-1190.

P-11 Kinetics modeling by non-linear regression method for the sorption of lead (II) ion onto a biomaterial
1Oboh,

I. O., 2Aluyor, E. O., 2Audu, T. O. K., 3Bassey, E. N.and 1Yesufu, S. O. of Chemical and Petroleum Engineering, University of Uyo, Uyo, Nigeria. 2Department of Chemical Engineering, University of Benin, Benin, Nigeria. 3Department of Chemical and Petrochemical Engineering, Akwa Ibom State University, Mkpat Enin, Akwa Ibom State. Abstract The biosorption of lead (II) ions onto a biomaterial - Luffa cylindrica in its natural form has been studied. The biomaterial was characterized by surface area, scanning electron microscopy and Fourier Transform Infra Red (FTIR) spectrometer before and after biosorption. The kinetic nonlinear models fitted were Avrami, Pseudo-first order, Pseudo-second order, Elovich and Intra-particle diffusion. The analysis of R2 values and error functions were evaluated. The adsorption kinetics followed the Elovich chemisorption kinetic model, obtaining the following the rinitial adsorption rate, The R2 values obtained were 0.9976, 0.9994, 0.9998 and 0.9998 for 35, 50, 100 and 210 mg/L of initial concentration of Pb (II), respectively. The Ferror values were, 1.55, 0.81, 0.35 and 0.39 %, respectively. The R2 values obtained were 0.9950, 0.9990, 0.9990, 0.9960 and 0.9960 for 0.2, 0.4, 0.6, 0.8 and 1.0 g of biosorbent dosage of Pb (II), respectively. The Ferror values were, 2.27, 1.21, 1.16, 1.92 and 1.94 %, respectively.This low error functions (Ferror) for Luffa cylindrica biosorption capacity for Pb (II) places this biosorbent as one of the best adsorbents for removal of Pb (II) from aqueous effluents. Keywords: Chemisorption, biomaterial, error function, Luffa cylindrica, biosorbent Introduction The greatest demand for metal sequestration today comes from the need to immobilize the metals released to the environment through human technological activities. It has been established that dissolved heavy metals escaping into the environment pose a serious health hazard (Kuyucak and Volesky, 1990). A search for newer treatment technologies for removal of toxic metals from waste water has directed attention to biosorption. This novel approach is competitive, effective and cheap. Natural materials that are available in large quantities are potential to be used as low cost adsorbents which are widely available and are environment friendly, as they represent unused resources (Goyal et al., 2008). A wide variety of materials have been used in researches such as peat, lignite, diatomite, dolomite, bone char, zeolites, peanut hulls and a range of other natural materials (Richard, 2009).
1Department

Lead is number two on the Agency for Toxic Substance and Disease Registry (ATSDR) Top 20 List (Roberts, 1999). Lead is the 5th most utilized metal with a lot of applicants ranging from its use in pipes, drains and soldering materials. The major sources of lead include air pollution, ammunition, batteries, canned foods, ceramics, chemical fertilizers, cosmetics, dolomite, dust, foods grown around industrial areas, gasoline, hair dyes and rinses, leaded glass, newsprint, and colored advertisement, paints, pesticides, pewter, pottery, rubber toys, soft coal, tap water, tobacco smoke etc. (International Occupational Safety and Health Information Center, 1999; ATSDR, 1995; Gary, 2004). An investigation dealt with the abatement of Pb (II) ions from aqueous system using Saraca indica leaf powder (SILP). The manuscripts also reported the applicability of leaf biomass for Pb (II) metal ion recovery and regeneration of the exhausted biosorbent thereby making the process more economical, beneficial and cost effective (Goyal et al., 2008). The fruits of Luffa cylindrica are smooth and cylindrical shaped. It is a lignocellulosic material which is composed of 60% cellulose, 30% hemicellulose, and 10% lignin (Mazali and Alves, 2005). They have a long history of cultivation in the tropical countries of Asia and Africa. Indo-Burma is reported to be the center of diversity for sponge gourd. The main commercial production countries are China, Korea, India, Japan and Central America (Bal et al., 2004). The use of sorption kinetics models such as, Pseudo-first order, Pseudo-second order, and many others will help to study the biosorption kinetics of Pb 2+ onto Luffa cylindrica seeds and sponge mixture. Modeling of biosorption kinetics data is important for predicting and comparing biosorption performance (Sahmoune et al., 2008). In the present study, a comparison was made of the various error functions for some selected experimental conditions and a trial-and-error nonlinear method of some widely used kinetic models for the biosorption of Pb2+ onto Luffa cylindrica seeds and sponge mixture. 2.0 Materials and Methods 2.1 Preparation of biomaterial The seeds and sponges of L. cylindrica were gathered into a clean plastic bag. They were dried in the oven at 105oC for 24 hours and afterwards ground with a grinding mill. The ground seeds and sponges were sieved and were of particle size 0.3 to 0.6mm. This was to allow for shorter diffusion path, resulting in a higher rate of biosorption (Adeyinka et al., 2007). The ground seed and sponge were mixed at a ratio of 1:1. 2.2 Preparation of aqueous solutions Stock solution of lead was prepared with distilled water and lead (II) trioxonitrate (V). The working solution was obtained by diluting the stock solutions with distilled water. The pH of the solution was adjusted to the pH of 6. The concentration of metal ions in solutions was analyzed by Atomic Absorption Spectrophotometer. A duplicate was analyzed for every sample to track experimental error and show capability of reproducing results (Marshall and Champagne, 1995). 2.3 Fourier Transform Infra Red analysis Fourier transform infrared spectroscopy (FTIR) of the adsorbent was done by using an FTIR spectrometer (Model FTIR 2000, Shimadzu, Kyoto, Japan). About 150 mg KBr disks containing approximately 2% of Luffa cylindrica sample was prepared shortly before recording the FTIR spectra in the range of 400 4000.0 cm-1 and with a resolution of 4 cm-1. The resulting spectra were average of 30 scans. 2.4 Surface area The surface area of the Luffa cylindrica sample was determined using Flowsorb 2300 manufactured by Micrometrics Instrument Corporation, USA. Krypton gas was used in

conducting single-point surface area measurements. Liquid nitrogen was used in setting the adsorption of nitrogen gas by the samples. The Luffa cylindrica was degassed at 100oC for 30 minutes and were cooled to liquid nitrogen temperature. The surface area of the sample under measurement was then read from the display-meter. The value of the surface area recorded was then converted to specific surface area (m2/g) by dividing the reading on the display by the weight of the Luffa cylindrica sample. 2.5 Biosorption Experiment The biosorption studies for evaluation of the Luffa cylindrica mixture for removal of the selected heavy metals from aqueous solutions was carried-out in triplicate using the batch biosorption procedure (Brasil et al., 2006; Lima et al., 2007 ). For these experiments, fixed amount of adsorbents (1000.0 mg) were placed in 250 ml conical flasks containing 50.0 ml of heavy metal solutions, which were agitated for a suitable time (5 to 120 mins) at 25 0C. Subsequently, in order to separate the adsorbents from the aqueous solutions, the flasks were centrifuged at 2400 rpm for 10 minutes. The final concentrations of the heavy metals remaining in the solution were determined by atomic absorption spectrophotometer (AAS). The amount of the metal ion sorbed and percentage of removal of metal ion by the biosorbent were calculated by applying the Equations (1) and (2), respectively: .V (-C)f m C qo = (1) .100 (-C) % Removal f
o o

C C
=

(2) where q is the amount of metal ion sorbed by the biosorbent (mg/g); C0 is the initial ion concentration put in contact with the biosorbent (mg/L), Cf is the final concentration (mg/L) after the batch biosorption procedure, V is the volume of aqueous solution (L) put in contact with the biosorbent and m is the mass (g) of biosorbent. 2.6 Kinetic studies The kinetic equations, which are, Avrami (Lopes et al., 2003), pseudo first-order (Largegren, S., 1898), pseudo-second order (Ho, Y.S., Mckay, G.M., 1999), Elovich (Ayoob et al., 2008) and intra-particle diffusion model (Weber Jr. and Morris, 1963) are given in Table 1. Table 1: Kinetic adsorption models Kinetic model Equation Pseudo-first-order (Largegren, S., 1898) Pseudo-second-order (Ho, Y.S., Mckay, G.M., 1999) Elovich (Ayoob et al., 2008) Avrami (Lopes et al., 2003)

.[1 - exp(-k . )] P q q t t e = t q 1 kq 1 q t
e 2 te

=+

q t t ln L 1 ln(ML) L 1
=+

. (1 - exp[-(k . )] ) AV
nAV

q=qt Intra-particle diffusion (Weber Jr.and Morris, 1963) q k t C t id = + 2.7 Evaluation of the kinetic parameters A trial and error was used for nonlinear regression to minimize or maximize the objective function using the solver add-in function, Microsoft Excel, Microsoft Corporation. In addition, the models were also evaluated by a percentage error function (Passos et al., 2007; Jacques et al., 2008), which measures the differences (%) of the amount of the divalent metal ions uptaken by the biosorbent predicted by the models and the actual q measured experimentally:
te

r
p i 2 exp mod exp

1 1 F (%) = 100 x . qp qq
error i erimental

(3) where qi model is each value of q predicted by the fitted model and qi experimental is each value of q measured experimentally, and p is the number of experiments performed. 2.8 The analysis of the impact of various error functions Six different error functions namely R2, HYBRID, MPSD, ERRSQ, ARE and EABS were optimized by non-linear regression method to minimize the error distribution between the experimental equilibrium data and the kinetic models studied to analyze the impact of various error functions on the predicted kinetic model. The explanations of various error functions used are given in Table 2.
i el i erimental

Table 2: Explanation of different error functions (Kumar et al., 2008) Error functions Definition/expression The coefficient of determination

r
22 2

(-)(-) (-)
isotherm calc isotherm calc isotherm calc

qqqq qq
+

The sum of the squares of the errors (ERRSQ)

r
1 2 ,, p i
=

(-) qq

e calc e isotherm i

The hybrid error functions (HYBRID)

i n i e isotherm e isotherm e calc

q qq npr
1, 2

(-) 100
,,
=

The average relative error (ARE)

i p i e isotherm e calc e isotherm

q qq nr
1, ,,
=

100 -

Results and discussion Table 3: Physical properties of the Luffa cylindrica biosorbent
Specific surface area - BET 0.28 m/g Total Surface area 1.1895 m/g Pore Diameter Range 1051.309204 to 0.003577 Tm Bul k de n s i t y 0.34 g /cm3

Table 3 shows the bulk density, surface area and pore diameter range for the biosorbent used

for this study. The Specific surface area using the BET method was 0.28m/g and the Pore diameter range was between 1051.309204 to 0.003577Tm. The bulk density was 0.34g /cm3. As observed, the surface area for the seed and sponge mixture of L. cylindrica is relatively low, with pore diameter values in agreement with those found for typical mesoporous materials (Hamoudi and Kaliaguine, 2003). (a) (b) Figure 2: FTIR spectrum of the mixture of seed and sponge of L. cylindrica biosorbent (a) before and (b) after biosorption. Figures 2 (a) and (b) show the FTIR spectral. The functional groups on the binding sites were identified by FTIR spectral comparison of the free biomass with a view to understanding the surface binding mechanisms. The significant bands obtained are shown in Figures 2 (a) and (b) Functional groups found in the structure include carboxylic, alkynes or nitriles and amine groups (Pavia et al., 1996). The stretching vibrations of C-H stretch of -CHO group shifted from 2847.05 to 2852.46 after Pb2+ biosorption. The assigned bands of the carboxylic, amine groups and alkynes or nitriles vibrations also shifted on biosorption. The shift in the frequency showed that there was biosorption of Pb2+ on the L. cylindrica biosorbent and the carboxylic and amine groups were involved in the sorption of the Pb2+ (Volesky, 2003). Table 4a:Kinetic parameters for Pb(II) using L. cylindrica as biosorbent Kinetic model Parameters Concentration (mg/L) 35.0 50.0 100.0 210.0 Pseudo-first-order qe (mg/g) 1.6863 2.2465 4.6644 10.152 kf (min-1) 0.7830 0.5820 0.7538 0.8808 R2 0.9958 0.9980 0.9988 0.9997 Ferror (%) 2.01 1.42 1.10 0.52 Pseudo-second-order qe (mg/g) 1.6973 2.2744 4.7015 10.192 ks(g/mg/min) 3.0117 1.2238 1.0672 0.9844 R2 0.9966 0.9993 0.9996 0.9999 Ferror (%) 1.80 0.84 0.63 0.28 Elovich M(mg/g/min) 1x1020 1x1019 3x1028 2x1020 L(g/mg) 31.555 22.555 15.404 10.620 R2 0.9976 0.9994 0.9998 0.9998 Ferror (%) 1.55 0.81 0.35 0.39 Intra-particle diffusion Ki(mg/g min-0.5) 0.0098 0.0148 0.0194 0.0203 C 1.6200 2.1400 4.5300 10.010 R2 0.9984 0.9991 0.9998 0.9999 Ferror (%) 1.26 0.98 0.40 0.24 Avrami qe (mg/g) 1.6836 2.2465 4.6644 10.152 Ka(min-1) 0.9693 0.8357 0.9511 1.0281 na 0.8078 0.6964 0.7926 0.8267 R2 0.9958 0.9980 0.9988 0.9997 Ferror (%) 2.01 1.42 1.10 0.52 Table 4b: Kinetic parameters for Pb(II) using L. cylindrica as biosorbent Kinetic model Parameter Dosage (g) 0.2 0.4 0.6 0.8 1.0 Pseudo-first-order qe(mg/g) 23.18 11.55 7.784 6.017 4.703

kf(min-1) 0.315 0.400 0.352 0.255 0.422 R2 0.971 0.976 0.976 0.967 0.981 Ferror (%) 5.47 5.00 5.18 6.50 4.44 Pseudo-second-order qe(mg/g) 24.15 11.97 8.089 6.316 4.847 ks(g/mg/min) 0.028 0.076 0.096 0.078 0.222 R2 0.988 0.991 0.992 0.993 0.991 Ferror (%) 3.47 3.10 2.89 3.02 2.89 Elovich M(mg/g/min) 48816 6 x105 78931 1291 4 x106 L(g/mg) 0.613 1.511 2.036 1.966 4.359 R2 0.995 0.999 0.999 0.996 0.996 Ferror (%) 2.27 1.21 1.16 1.92 1.94 Intra-particle diffusion Ki(mg/g min-0.5) 0.573 0.236 0.171 0.172 0.081 C 18.79 9.814 6.491 4.653 4.100 R2 0.995 0.999 0.998 0.989 0.996 Ferror (%) 2.49 0.86 1.59 3.55 1.96 Avrami qe(mg/g) 23.18 11.55 7.784 6.017 4.703 Ka(min-1) 0.513 0.577 0.542 0.461 0.711 na 0.615 0.693 0.650 0.554 0.593 R2 0.972 0.976 0.976 0.967 0.981 Ferror (%) 5.47 5.00 5.18 6.50 4.44 It should be noted that only the analysis of R2 values to establishment of a given model is not enough, because the error function evaluates the differences associated with each individual point fitted by the model in relation to each experimental point measured. On the other hand the R2 value measures the differences associated with each individual point in relation to the average fitted curve (Passos et al., 2008; Jacques et al., 2007). Table 4a show the differences of the R2 and the Ferror values could be visualized for Pb (II) Elovich kinetic model for the four levels of concentration (see Table 4a). The R2 values obtained were 0.9976, 0.9994, 0.9998 and 0.9998 for 35, 50, 100 and 210 mg/L of initial concentration of Pb (II), respectively. The Ferror values were, 1.55, 0.81, 0.35 and 0.39 %, respectively. It should be stressed that the best R2 value obtained with the more initial concentration of Pb(II) (100 mg/L) led to the lowest error (0.35%), conversely, with the lowest initial concentrations of Pb(II), the value of R2 were little bit worse, but with highest value of error function (1.55%). Table 4b show the differences of the R2 and the Ferror values could be visualized for Pb (II) Elovich kinetic model for the five levels of biosorbent dosages. The R2 values obtained were 0.9950, 0.9990, 0.9990, 0.9960 and 0.9960 for 0.2, 0.4, 0.6, 0.8 and 1.0 g of biosorbent dosage of Pb (II), respectively. The Ferror values were, 2.27, 1.21, 1.16, 1.92 and 1.94 %, respectively. It can be concluded that the R2 value 0.999 for biosorbent dosage 0.6g with Ferror of 1.16% could be the best from the rest even though they have the same R2 value. These results reinforce the need of using a statistical error function to better evaluate the adsorption models, as previously reported (Passos et al., 2008; Jacques et al., 2007). Conclusion A kinetic study was carried out and the experimental data fitted into Pseudo-first order, Pseudosecond order, Intra-particle diffusion, Elovich and Avrami models. The present study shows nonlinear regression method as a best way to obtain both the kinetic and isotherm parameters and

also to select the optimum isotherm and kinetic model. The present investigation suggests that the size of error function alone is not a deciding factor to select the optimum kinetic model. In addition to the size of coefficient of determination, the validation of the theory behind the kinetic model should be verified with the help of experimental data while selecting the optimum kinetic model. The sorption of Pb(II) onto Luffa cylindrica for both Initial ion concentration and biosorbent dosages followed the Elovich chemisorptions model. References Adeyinka A, Liang H, Tina G (2007). Removal of Metal Ion form Waste Water with Natural Waste. School of Engineering and Technology. 1-8(33): 4. ATSDR (1995). Agency for Toxic Substance and Disease Registry. Atlanta, G.A. ATSDR (1999). Agency for Toxic Substances and Disease Registry Tox FAQs for lead CAS. 7439-92-1Atlanta GA. Bal K. J., Hari B. K. C., Radha K., Ghale G. M., Bhuwon R.S., Madhusudan P.U.(2004) Descriptors for Sponge Gourd [Luffa cylindrica (L.) Roem.], NARC, LIBIRD & IPGRI. Basil JL, Ev RR, Milcharek CD, Martins LC, Pavan FA, dos Santos, Jr. AA, Dias SLP, Dupont J, Norea CPZ, Lima EC (2006). Statistical Design of Experiments as a tool for optimizing the batch conditions to Cr(VI) biosorption on Araucaria angustifolia wastes. J Hazard Mater; 133: 143-153. Dupler, D. (2001). Heavy metal poisoning Gale encyclopedia of Alternative Medicine Farmington Hills MI. Gale Group. Gary, F. (2004). The Hair Tissue Mineral Analysis / Why Heavy Metals are a Hazard to Your Health. http://www.becomehealthynow.com/article/productshair/122/5/ .Last Updated July, 15, 2004. Goyal, P., Sharma, P., Srivastava, S, Srivastava, M. M.( 2008). Saraca indica leaf powder for decontamination of Pb: removal, recovery, adsorbent characterization and equilibrium modeling, International Journal of Enviornmental Science and Technology, Vol. 5, No. 1, pp. 27-34. Ho, Y.S., Mckay, G.M. (1999).Pseudo-second order model for sorption process, Proc. Biochem. 34: 451465. International Occupational Safety and Health Information Centre (1999): Metals. In Basics of Chemical Safety Chapter 7. Geneva. International Labour Organization. Jacques, R.A. Bernardi, R. Caovila, M. Lima, E.C. Pavan, F.A. Vaghetti, J.C.P. Airoldi, C. (2007). Removal of Cu (II), Fe(III) and Cr(III) from aqueous solution by aniline grafted silica gel, Separation Science and Technology. 42; 591609. Kumar, K.V., Porkodi, K., Rocha, F. (2008).Isotherms and thermodynamics by linear and nonlinear regression analysis for the sorption of methylene blue onto activated carbon: Comparison of various error functions. Journal of Hazardous Materials. 151, 794804. Kuyucak, N. and Volesky, B. (1990).Biosorption by algal biomass, Biosorption of heavy metals, B. Volesky (Editor), CRC Press, Boca Raton, FL, pp. 173-198. Largegren,S.(1898) About the theory of so-called adsorption of soluble substances, Kungliga Suensk Vetenskapsakademiens Handlingar 241: 139. Lima, E. C., Royer, B., Vaghetti, J.C.P., Brasil, J.L., Simon, N.M., dos Santos Jr., A.A., Pavan, F.A., Dias, S.L.P., Benvenutti, E.V. and da Silva, E.A. (2007). Adsorption of Cu(II) on Araucaria angustifoliawastes: determination of the optimal conditions by statistic designof experiments, J. Hazard. Mater. 140, 211220.

Lopes, E.C.N., dos Anjos, F.S.C., Vieira, E.F.S., Cestari, A.R.(2003). An alternative Avrami equation to evaluate kinetic parameters of the interaction of Hg(II) with thin chitosan membranes, J. Colloid Interface Sci. 263: 542547. Marshall, W. E. and Champagne, T.E. (1995). Agricultural Byproducts as Adsorbents for Metal ions in Laboratory Prepared Solutions and in Manufacturing Wastewater, Journal of Environmental Science and Health, Part A: Environmental Science and Engineering. Vol. 30, No. 2, 241 261. Mazali I.O. Alves O.L. (2005). Morphosynthesis: high fidelity inorganic replica of the fibrous network of loofa sponge (Luffa cylindrica). Anais da Academia Brasileira de Cincias, Vol. 77, No. 1, p. 25-31. Passos, C.G. Lima, E.C. Arenas, L.T. Simon, N.M. da Cunha, B.M. Brasil, J.L. Costa, T.M.H. Benvenutti, E.V. (2008). Use of 7-amine-4-azahepthylsilica and 10-amine4-azadecylsilica xerogels as adsorbent for Pb(II). Kinetic and equilibrium study, Colloids Surfaces. A 316; 297306. Pavia, D.L., Lampman, G.M., Kriz, G.S. (1996). Introduction to Spectroscopy, 2nd edn., Saunders Golden Sunburst Series, New York. Sahmoune, M.N., Louhab, K. and Boukhiar, A. (2008) Kinetic and equilibrium models for the biosorption of Cr (III) on streptomyces rimosus . Research Journal of Applied Sciences 3(4), 294-301. Volesky, B. (2003) Sorption and Biosorption. Montreal-St. Lambert, Quebec, Canada, BV Sorbex Inc., 316 p. ISBN 0-9732983-0-8. Weber Jr., W.J., Morris, J.C. (1963). Kinetics of adsorption on carbon from solution, J. Sanit. Eng. Div. Am. Soc. Civil Eng. 89: 3159. WHO (1998) Aluminum. In Guideline for Drinking-water Quality, second Edition Health criteria and other supporting information addendum to volume pp3-13 Geneva: World Health Organization. P-12 OPTIMIZATION OF NATURAL GAS PIPELINE NETWORK USING THE COMBINED
GENERALIZED REDUCED GRADIENT AND MULTI-START METHOD

Ambrose N. Anozie*, Udeme O. Eton Applied Thermodynamics and Process Design Research Laboratory Department of Chemical Engineering, Obafemi Awolowo University, Ile-Ife, Osun state, Nigeria *Corresponding Author, Email: ananozie@yahoo.com; Tel.: +2348034066080 Abstract An optimization-oriented framework for modeling natural gas transportation network is presented in this work. The objective function is the transportation cost including the capital and operating costs of the network. The decision variables are: suction and discharge pressure at the compressor stations, length and diameter of the pipeline segments. A methodology based on the combined large scale generalized reduced gradient and multi-start method is adopted for the design of a proposed natural gas pipeline network. The combined method is implemented by means of an EXCEL-based optimizer. This spreadsheet based approach provides an efficient, highly interactive and easily used solution scheme for industrial applications. A cost savings of 36.4% was achieved in the optimal configuration with only 3 compressor stations remaining out of the 10 possible compressor stations in the initial configuration. Keywords: Natural gas, pipeline network, transportation cost minimization, decision variables, constraints, combined optimization method. 1. Introduction

Natural gas, viewed as a cleaner-burning alternative to other fossil fuels (coal and crude oil) in terms of acid and greenhouse gas pollution, is increasingly being used as an energy source; and by most estimates, its global consumption will double by 2030 (Riva et al., 2006). The means of transporting natural gas to the end users has remained a key challenging aspect (both in terms of technology and economics) of meeting the steeply growing demand for the resource. Pipeline is the principal and most convenient method of transporting natural gas; either from an offshore location to onshore for processing or to interface with existing distribution grids. It accounts for 75% of the total volume of gas transported in the world (Economides et al., 2005). The capital and operating costs associated with pipeline transportation are very huge such that even a marginal improvement in the design and operation of the system can result in substantial cost savings. Consequently, there has been a growing interest in reducing these costs. A natural gas pipeline network (NGPN) is composed of sources of gas, pipelines, compressor stations and delivery terminals. The design of a NGPN involves both capital expenditures and continuous operating expenditures. The capital cost is largely dependent on the costs of pipes and compressors (Edgar et al., 2001). The cost of pipes depends on the pipe length and diameter, whereas the cost of compressors is related to compressor horsepower (Mokhatab et al., 2006). As the gas flows through the network, its pressure (and energy) decreases due to both frictional losses and heat transfer between the gas and its surrounding. The most significant part of the operating cost is the cost of fuel (or energy) consumed by the compressor stations in order to boost the lost pressure of the pipeline gas (Wu et al., 2000; Villalobos-Morales et al., 2003). These compressor stations consume for operation part of the transported gas, resulting in fuel consumption cost and a significant contribution to CO2 emission. It is estimated that the compressor stations typically consume about 3 5% of the transported gas (Borraz-Snchez and Ros-Mercado, 2009; Borraz-Snchez and Ros-Mercado, 2004; Ros-Mercado et al., 2002). Investigations on various pipeline systems indicated that the operating cost of the compressor stations represent between 25 50% of the total companys operating budget (Luongo et al., 1989). Two main approaches that are classically encountered in gas network representations are numerical simulation and optimization. The main purpose of simulation is to determine the actual behaviour of NGPN under given conditions. Simulation has two disadvantages. First, finding an adequate flow regime can take a large number of runs and secondly, it cannot ensure that the solution achieved is optimal. This explains mainly why the searching process must be substituted with more sophisticated algorithms. Optimization generally works with simplified models, but it yields optimum results where limits or certain target values will be achieved automatically if they are defined as optimization constraints. The optimization of the design of a NGPN involves numerous variables which include: number of compressor stations, location of the compressor stations, pipeline length, pipeline diameter, suction and discharge pressures at the compressor stations, operating pressure, temperature and flow rate of the gas in the pipeline (Omar et al., 2010). Each of these parameters influences the overall cost of the NGPN to some degree. NGPN optimization problems are intrinsically very difficult to solve. The difficulties of NGPN problems arise from several aspects. First, compressor stations are very sophisticated entities themselves. They might consist of a few dozen of compressor units with different configurations and characteristics. Each unit could be turned on or off, and its behaviour is non-linear. Second, the set of constraints that define feasible operating conditions in the compressors and along the pipes constitute a very complex system of non-linear constraints. Third, the considered optimization problem may

involve both continuous and integer variables, and use of a mixed integer non-linear programming formulation. Moreover, the treatment of industrial-size problems may render the problem highly combinatorial. An extensive literature on the optimization approach to NGPN has been published over the past 30 years. An excellent compilation of these research efforts is presented by Chebouba et al. (2009), and BorrazSnchez and Haughland (2010). Analysis of the dedicated literature reveals that most of the methods developed are based on dynamic programming (DP) and gradient search techniques (generalized reduced gradient); however few researchers have used metaheuristic techniques to optimize NGPN problems. The principal advantages of DP are that a global optimum is guaranteed and that the non-linearity can be easily treated. However, its application is practically limited to simple network topologies (linear or ramified) and also the level of computation increases exponentially with problem dimension. The advantages of generalized reduced gradient (GRG) method are that dimension is not a problem and that it could be applied to cyclic network schemes. The drawback with GRG method is that, since it is a gradient search method there is no guarantee to find a global optimum for a non-convex problem. Although the metaheuristic methods can give good results, there is no guarantee of optimality. In the present work, a methodology based on combined large scale generalized reduced gradient (LSGRG) and multi-start method is adopted for the optimization of NGPN problem. From the optimization perspective, the NGPN optimization problem is modelled as a non-linear problem (NLP) where the cost function is typically non-linear and non-convex, and some of the constraints are non-convex as well. The application of NLP algorithms such as generalized reduced gradient (GRG) alone to non-convex problems usually lead to convergence to the nearest local minimum which may not be the global minimum. The application of global optimization methods such as multi-start method guarantees that the global optimum is obtained. The combined method is employed for the design of a proposed NGPN. Four decision variables are to be determined for the network, they include: the suction and discharge pressure at each compressor station, the length and diameter of each pipeline segment. The combined method is implemented by means of an Excel-based optimizer. This spreadsheet based approach provides an efficient, highly interactive and easily used solution scheme for industrial applications. 2. Problem Definition The initial configuration of the proposed pipeline network is shown in Figure 1. The NGPN is defined by the set of all nodes N, the set of compressor station nodes N c, the set of supply nodes Ns (representing the sources), the set of demand nodes N d (representing the delivery terminals), and the set of pipeline segment arcs Ap. Each compressor station is represented by a node, i, and each pipeline segment by an arc, j. Each pipeline segment is associated with the following variables: (i) the gas flow rate, Q, (ii) the discharge pressure of the compressor, Pd, (iii) the suction pressure of the compressor, Ps, (iv) the pipeline diameter, D, and (v) the pipeline length, L. Figure 1: Initial configuration of the proposed Natural Gas Pipeline Network The flow rate is fixed at the inlet of the network and each compressor station is assumed to have consumed for operation 4% of the gas transmitted, hence only the last four variables (P d, Ps, D, L) are to be determined (decision variables) for each segment. The subject of this work is the minimization of the transportation costs (including capital cost and operation cost) of the NGPN.

The problem can thus be formulated as: for a given gas flow rate at the inlet of the network with certain pressure conditions, and one at the delivery terminals with pre-assigned pressures at the end of the lines, what is the optimal combination of the decision variables. 2.1 Objective function The cost objective function, Equation 1, is derived from the summation of three cost items, namely: the annual operating cost of the compressor stations, the annualized capital cost of the compressor stations, and the annualized capital cost of the pipeline segments; in conjunction with the expression for compressor brake horsepower given by Guo and Ghalamber (2005). Minimize

( )
==

+ =+
P i i i cA

j jj zw s d i ii N i

CLD P P

w QT CCC
1 3 1

1 0.08537076
12

(1) where C is the transportation cost (US$/yr); C1 and C2 are unit costs (US$/hp.yr) of annual operating cost and annualized capital cost of compressors, respectively; C 3 is unit cost (US$/inch.mile) of annualized capital cost of pipeline segments; Q i is the gas flow rate of natural gas into compressor station i, expressed in million standard cubic feet per day (MMSCFD); P di and Psi are discharge and suction pressure (psia) of compressor i, respectively; w is a constant that depends on the nature of gas transported; Zi and Ti are the compressibility factor and temperature (R) of the gas at the suction of compressor i, respectively; Ni is the adiabatic efficiency of compressor i; Dj and Lj are diameter (inch) and length (mile) of pipeline segment arc j, respectively. 2.2 Constraints It is necessary to take into consideration several constraints that establish the feasible operating domain of the NGPN. These constraints represent the mathematical model for the NGPN and are based on the configuration and basic elements of the network. They are developed based on the knowledge of performance characteristics of the compressors and pipe flow analysis. (a) Physical constraint Compression increases the pressure of the gas but the pressure of the gas decreases along the pipeline segments. Consequently, the discharge pressure must be greater than or equal to the suction pressure for each compression station, however the compression ratio must not exceed a pre-specified maximum limit, r. 1
i i

s d

P P ; c i = 1,2,..., N (2a) r P P
i i

; c i = 1,2,..., N (2b) (b) Management constraint Upper and lower bounds are imposed on the four decision variables for each node and segment of the NGPN.
d U dd L di i i

P P P ; c i = 1,2,..., N (3a)
U ss L si i i

P P P ; c i = 1,2,..., N (3b)
U jj L j U jj L j

L L L ; p j = 1,2,..., A (3c)

D D D ; p j = 1,2,..., A (3d) where the superscripts L and U represent the lower and upper limits of the variables, respectively. The length of the NGPN is fixed, and with 5 pipe branches the following constraints result. 1 2 3 4 L + L + L + L = 46.90 (4a) 1 5 L + L = 50.03 (4b) 1 5 6 7 L + L + L + L = 96.83 (4c) 1 5 6 7 8 9 L + L + L + L + L + L = 138.4 (4d) 1 5 6 7 8 9 10 11 12 L + L + L + L + L + L + L + L + L = 175.3 (4e) (c) Flow constraint Pipe flow equation is one of the governing equations of a NGPN and it defines the relationship between the upstream pressure, downstream pressure and flow of gas in pipes. It is derived based on the principle of flow analysis of gas in pipelines. The flow of gas through pipelines can be affected by various factors such as properties of the gas, friction factor and geometry of the pipes, and operating conditions such as pressure and temperature. Several equations have been developed that describe the pipeline flow dynamics (McAllister, 1993). For this study, the Weymouth equation (Equation 5) is used due to its frequent and wide application in the natural gas industry for the design of small diameter pipeline system (D t 15 inch).
j ds

L PP Q D jj
jj 22 3 8

871 = (5) Equation 5 can be represented as functional form, where the representation consists of only parameters which are unknown in that equation. If the inlet and outlet pressures, diameter and length of each pipeline segment are unknown, the functional representation takes the form of Equation 6.
jj

()

sdjj

fPPDL

, , , = 0 (6) The application of Equation 5 involves some assumptions, namely: steady state flow and isothermal condition of the pipeline gas. The temperature of the pipeline gas is taken to be

constant at the average soil temperature. The pipeline network is assumed to be composed of long horizontal pipeline segments; kinetic energy changes and mechanical work are also negligible. 3. Materials and Methods 3.1 Pipeline mapping and route estimation The proposed natural gas pipeline network (NGPN) is a branched network topology receiving a specified quantity of natural gas from the source (Nigerian Gas Companys Facility in Port Harcourt, Rivers State, Nigeria) at some pressure condition and supplying it to five (5) terminal points (state capitals in South-Eastern Nigeria). Figure 2 shows the geographic map of the study area (South-Eastern States of Nigeria), which lies on: latitude 4o, 19, 23.46 N to 7o, 8, 11.95 N, and longitude 60o, 30, 43.124 E to 8o, 19, 50.00 E. The Geographic Information System (GIS) software, Arc GIS (version 9.3) is used for pipeline mapping in order to plot the route for the proposed natural gas pipeline network and estimation of the distances of the pipeline routes. The co-ordinate system used for Figure 2: Map of study area showing the proposed pipeline and existing pipelines in the surrounding area geo-referencing is the geographic co-ordinate system, the projection is world geodetic system and the datum is Minna in Nigeria. These three parameters (datum, projection and co-ordinate system) are to enable the geographic integrity to be maintained. The final map output is shown in Figure 2 which is on a scale of 1:2,000,000; and it shows the existing natural gas pipeline facilities as well as the proposed NGPN and also contains some peripheral information such as approximate route distance between terminals. 3.2 The combined large scale generalized reduced gradient (LSGRG) and multi-start method Although the formulation of Equation 1 involves integer variables, at each node and segment, the problem is a non-linear problem without integer variables. Because of the form of the objective function, if the ratio (Pdi/Psi) = 1, the term involving compressor i vanishes from the first summation in Equation 1. Hence, a NLP algorithm can be applied to solve Equation 1.The objective function (Equation 1) is a non-convex, non-linear problem since the objective function and flow constraint are non-linear functions of the decision variables. Optimization models with non-linear equality constraints are generally non-convex in nature (Edgar et al., 2001). The application of NLP algorithms such as generalized reduced gradient (GRG) alone to non-convex problems usually lead to convergence to the nearest local minimum which may not be the global minimum. The application of global optimization methods such as multi-start method will guarantee that the global optimum is obtained. The combined large scale generalized reduced gradient (LSGRG) and multi-start method is adopted as the solution algorithm for the NGPN optimization problem. A detailed explanation of the GRG method is left out here but can readily be accessed in public (Bazaraa et al., 1993). The advantages of the GRG method are also given in the literature (Bazaraa et al., 1993; Luenberger, 1989; Edgar et al., 2001; Reklaitis et al., 1983; Lasdon et al., 1978). Many GRG-based codes are available. The pioneering work can be traced back to Abadie (1972), and other researchers have developed their own GRG codes (Cohen, 1974). The optimizer termed Risk Solver Platform (version 11.0) developed by Frontline System Inc. (Internet, 2011) has an inbuilt LSGRG-based engine and is used for this work. It is fully compatible with Microsoft Excel; such spreadsheet solvers provide a user-friendly interface and an easy implementation platform for even large problems in practice.

Multi-start methods are a popular way to seek globally optimal solutions with the aid of a classical smooth nonlinear solver (that by itself finds only locally optimal solutions). The multistart method automatically starts the nonlinear solver from randomly selected multiple points, reaching different locally optimal solutions, then selects the best of these as the proposed globally optimal solution. With multi-start methods, as the number of runs of the nonlinear solver increases, the probability that the globally optimal solution has been found also increases towards 100%. Accordingly, multi-start method combined with LSGRG method will be an effective heuristic for the solver to locate the best-practice optimal solution (Edgar et al., 2001). 3.3 Implementation of the combined method in Excel-based Risk Solver Platform The optimization model is converted from the algebraic form to a spreadsheet form (solver model). (a) Building the solver model To use the Excel-based solver, a spreadsheet model is built that specifies: (i) The adjustable cells which hold the decision variables. These cells are changed by the solver toward optimizing the objective function. (ii) The target cell which hold the objective function formula. The target cell is minimized, maximized or set to target by the solver. The objective function cell must depend on the decision variable (adjusted) cells. (iii)The constraint cells To set up the optimization model as a Microsoft Excel spreadsheet, the following essential steps are taken. Step 1: Cell-allocation and formulation for the decision variables. The columns of Pdi, Psi, Lj and Dj denote the set of decision variables that the solver can change towards optimizing the objective function (target cell). The cells under these columns are reserved to hold the values of the decision variables for all the pipeline segments in the network. Step 2: Cell-allocation and formulation for the objective function . The column of target cell is used to represent the objective function. A formula to calculate the objective function (equation 1) value is entered in this cell. Step 3: Cell-allocation and Formulation for the Constraints. The column of Calc under the physical and flow constraint sections are used to hold the formula that calculate the left hand sides of Equations 2 and 6 (physical and flow constraints respectively). The right hand sides of these constraints were entered as numbers in adjacent columns called Spec in these sections. Other constraints were entered as numbers in other cells. (b) Defining the solver model Defining the optimization problem involves specifying the following to the solver: (i) the cells that are reserved for the decision variables, (ii) the cell that calculates the value of the objective function, (iii) the cells that calculate the constraints left hand sides, and (iv) the cells that hold values for the constraints right hand side, and bounds on the variables. The fully defined solver model for the NGPN will show cells that contain the decision variables, objective function and constraints. (c) Initial parameter specifications Figure 1 shows the initial configuration of the proposed NGPN, with ten (10) compressor stations and twelve (12) pipeline segments grouped into five (5) pipe branches. The maximum number of compressor stations in each pipe branch was set to two (2). The inlet pressure (P inlet)

and flow rate into the NGPN is fixed at 65 bar (942.7453 psia) and 15 MMSCFD (million standard cubic feet per day), respectively. The output pressures (P out) at the delivery terminals (state capitals) are fixed at 45 bar (652.6698 psia) in each case. The maximum allowable operating pressure (MAOP) in the network was fixed at 65 bar (942.7453 psia). The length of the pipe branches are constrained based on the distances of the routes involved as shown in Table 1. The upper and lower bounds on the diameter of the pipeline segments are set at 12 inches and 4 inches, respectively. A lower bound of 2 miles is placed on the length of the pipeline segments to ensure that the natural gas is at ambient conditions when it enters a subsequent compressor station in the network. Table 1: Distances of the proposed NGPN routes Route Description Distance (mile) 1 PortHarcourt Owerri 50.03 2 PortHarcourt Aba 26.90 3 Owerri Awka 46.80 4 Awka Enugu 41.52 5 Enugu Abakaliki 36.97 4. Results and Discussion The proposed NGPN is a 202.22 mile-long pipeline system with delivery terminal in each of the five South-Eastern state capitals. Figure 3 shows the optimal configuration of the proposed NGPN. Comparison of the optimal configuration in Figure 3 with the initial configuration in Figure 1 shows the improvement made by the optimization method. The optimal configuration of the NGPN has only three (3) compressor stations out of the ten (10) possible compressors. The Microsoft Excel template of the optimal solution of the NGPN optimization problem will also be shown on the spreadsheet. From an initial configuration with 10 compressor stations, the solver reduced the objective function from the first feasible state of US$ 11,107,782.05/year to US$ 7,068,389.01/year, achieving a savings of US$ 4,039,393.04/year. This reduction represents a 36.4 % cost savings over the cost of the initial configuration. The values of the four decision variables are presented in Table 2 and the optimal values of the pressures at the compressor stations are shown in Table 3. The suction and discharge pressures for compressor stations 1, 2, Figure 3: Optimal configurations of the proposed NGPN 3, 5, 7, 9 and 10 are identical, hence the compression ratio for these compressor stations all have the value of 1.0. This implies that these compressor stations are not necessary in the NGPN as there was no significant compression of the gas; hence compressor stations 1, 2, 3, 5, 7, 9 and 10 do not exist in the optimal configuration. The three (3) compressor stations remaining in the network (compression stations 4, 6 and 8) have a compression ratio of 1.3 each. This result is in collaboration with the data reported by Guo and Ghalambor (2005), which indicated that the best compression ratio for natural gas transmission lines lies between 1.3 and 1.4. According to Mokhatab et al. (2006), the pipeline network should be operated as close to MAOP as possible to enhance its efficiency. Table 2 shows that the values of the operating suction pressures at the pipeline segments are within 10.7% of the MAOP. 5. Conclusions In this paper a model for the minimization of the transportation cost of natural gas pipeline network was studied. The decision variables are suction and discharge pressures at compressor stations, length and diameter of pipeline segments. A total of twelve constraints including physical, management and flow constraints were considered. The solution method used is the combined LSGRG and multi-start algorithm which guarantees that a global optimum is

found. The method was implemented in the widely accepted spreadsheet environment, EXCEL, and was applied to optimize the design of a proposed NGPN to transmit natural gas from PortHarcourt to five South-Eastern states of Nigeria. Table 2: Values of design variables for the optimal NGPN configuration Pipeline segment, j Suction Pressure (psia) Discharge Pressure (psia) Length (mile) Diameter (inch) Gas Flowrate (mmscfd) 1 942.7453 841.4712 40.9 8 15 2 841.4760 841.4712 2 4 2.4 3 844.8563 841.4712 2 4 2.304 4 844.8821 652.6698 2 4 2.212 5 925.0581 652.6698 9.13 8 12 6 844.8614 841.4712 2 8 9.119 7 842.2812 652.6698 44.8 4 8.754 8 842.9723 841.4712 39.52 4 6.004 9 843.8899 652.6698 2 4 5.763 10 844.5957 841.4712 2 4 3.132 11 844.6936 841.4712 2 4 3.007 12 844.7259 652.6698 32.97 4 2.887 Table 3: Optimal pressure level at the compressor stations Compressor Station, i Suction Pressure Discharge Pressure Compression ratio, r 1 841.4712 841.4760 1.0 2 841.4712 844.8563 1.0 3 841.4712 844.8821 1.0 4 652.6698 844.8614 1.3 5 841.4712 842.2812 1.0 6 652.6698 842.9723 1.3 7 841.4712 843.8899 1.0 8 652.6698 844.5957 1.3 9 841.4712 844.6936 1.0 10 841.4712 844.7259 1.0 The results showed that the optimal configuration retained only 3 compressor stations out of the 10 possible compressor stations in the initial proposed configuration, and hence the transportation cost of the optimal network was reduced by 36.4 %. Each of the retained compressors has a compression ratio of 1.3 which is within the range of values recommended in the literature.

The numerical results obtained in this work indicate the viability of the use of the combined LSGRG and multi-start method for optimizing the design and operation of natural gas pipeline network. Moreover, engineers applying this spreadsheet-based approach do not require additional optimization knowledge, but effortless spreadsheet manipulation. References Abadie, J. (1972). Application of GRG algorithm to optimal control problems. In :J. Abadie, Nonlinear and integer programming. Amsterdam , North Holland. pp. 191-211. Bazaraa, M. S., Sherali, H. D. and Shetty, C. M. (1993). Nonlinear programming: theory and algorithms. 2nd ed. John Wiley and Sons, New York. Borraz-Snchez, C. and Ros-Mercado, R. Z. (2004). A non-sequential dynamic programming approach for natural gas network optimization. WSEAS Transactions on Systems. 3 (4): 13841389. Borraz-Snchez, C. and Ros-Mercado, R. Z. (2009). Improving the operation of pipeline systems on cyclic structures by tabu search. Computers & Chemical Engineering. 33 (1): 5864. BorrazSnchez. C. and Haughland, D. (2010). Minimizing fuel cost in gas transmission networks by dynamic programming and adaptive discretization. Computers & Industrial Engineering. (in press). Chebouba, A., Yalaoui, F., Smati, A., Amodeo, L., Younsi, K. and Tairi, A. (2009). Optimization of natural gas pipeline transportation using ant colony optimization. Computers & Operations Research. 36: 1916-1923. Cohen, C. (1974). Generalized reduced technique for non-linear programming user write up. Boston, MA: Vogelback Computing Center, North-Eastern University. Economides, M. J., Sun, K. and Subero, G. (2005). Compressed Natural Gas (CNG): An Alternative to Liquid Natural Gas (LNG). Paper presented at the Asia Pacific Oil and Gas Conference and Exhibition, Jakarta, Indonesia, (April, 57). Edgar, T. H., Himmelblau, D. M. and Lasdon, L. S. (2001). Optimization of chemical processes. 2nd ed. Mc-Graw Hill Companies Inc., New York. pp. 265-323, 461-478. Guo, B. and Ghalambor, A. (2005). Natural Gas Engineering Handbook. Gulf publishing Company, Houston, Texas, USA. ch. 2, 9, & 11. Internet http://www.frontsys.com or http://www.solver.com; accessed May 18, 2011. Lasdon, A. S., Warren, A. D., Jain, A. and Ratner, M. (1978). Design and testing of generalized reduced gradient code for nonlinear programming. ACM transactions on mathematical oftware. 4 (1): 34-50. Luenberger, D. G. (1989). Linear and nonlinear programming. 2nd ed. Reading , MA: AddisonWesley. Luongo, C. A., Gilmour, B. J. and Schroeder, D. W. (1989). Optimization in natural gas transmission networks: A tool to improve operational efficiency. Technical report, Stoner Associates, Inc., Houston. Retrieved on February 20, 2011. McAllister, E. W. (1993). Pipeline rules of thumb handbook. Gulf publishing company, Houston, Texas. Mokhatab, S., Poe, W. A., and Speight, J. G. (2006). Handbook of Natural Gas Transmission and Processing. Gulf Professional Publishing. USA. ch. 1 & 10. Omar Fayez Mohamed, El-Mahdy, Mohamed Ezz Hassan Ahmed, and Sayed Metwalli. (2010). Computer aided optimization of natural gas pipe networks using genetic algorithm. Applied Soft Computing. 10: 1141-1150.

Reklaitis, G. V., Ravindran, A. and Ragsdell, K. M. (1983). Engineering optimization: methods and applications. John Wiley and Sons, New York. Ros-Mercado, R. Z., Wu, S., Scott, L. R. and Boyd, E. A. (2002). A reduction technique for natural gas transmission network optimization problems. Annals of Operations Research. 117 (14): 217234. Riva A., Angelosante, S. D. and Trebeschi, C. (2006). Natural gas and the environmental results of lifecycle assessment. Energy. 31 (1): 138-148. Villalobos-Morales, Y., Cobos-Zaleta, D., Flores-Villarreal, H. J., Borraz-Snchez, C. and RiosMercado, R. Z. (2003). On NLP and MINLP formulations and preprocessing for fuel cost minimization of natural gas transmission networks. In: Proceedings of the 2003 NSF design, service and manufacturing grantees and research conference, Birmingham, USA. Wu, S., Ros-Mercado, R. Z., Boyd, E. A. and Scott, L. R. (2000). Model relaxations for the fuel cost minimization of steady-state gas pipeline networks. Mathematical and Computer Modelling. 31 (23): 197220. P-13 INVESTIGATION INTO THE COMPETITIVE INHIBITION OF HYDROCARBON DEGRADATION IN POND SYSTEM FOR WET SEASON UPON THE INFLUENCE OF MOMENTUM TRANSFER
Ukpaka1, C. P; Ogoni2, H.A and Nnadi3, V.G
Department of Chemical/Petrochemical Engineering Rivers State University of Science and Technology Nkpolu, P. M. B. 5080, Port Harcourt, Nigeria. e-mail: chukwuemeka24@yahoo.com 2 Niger Delta University Wilberforce Island Bayelsa State, Nigeria. 3 Total E $ P Nigeria Limited, plot 25 Trans Amadi Industrial Layout, Port Harcourt, Nigeria, Port Harcourt, Nigeria. e- mail: vincent. nnadi@total.com
1

Abstract This study was based on examining the competitive inhibition of hydrocarbon degradation in pond system upon the influence of momentum transfer. The overall objective was to establish effectiveness of the competitive inhibition of individual hydrocarbon degradation upon the continuous discharge of wastewater in pond system undergoing bioremediation .Mathematical model was developed to determine the influence of momentum on competitive inhibition of individual hydrocarbon degradation in pond system for wet season. Mathematical technique known as separation of variable was applied to the general solution from the hydrodynamic model. The results obtained revealed decrease in the individual hydrocarbon concentration with increase in distance and time. Similarly, decrease in the rate of momentum transfer of substrate was observed with increase in distance. The variation in the individual hydrocarbon concentration can be attributed to the variation in momentum transfer, distance as well as physicochemical parameters of wastewater discharged into the pond system. This work therefore present comprehensive and feasible models for monitoring and predicting the rates of individual substrate concentration gradient upon the influence of momentum transfer and individual relationship of substrate inhibiting one another in the pond system. 1. Introduction The current worldwide complain against environmental degradation has attracted the attention of environmentalist, geoscientist, engineers etc. The exploration, production, transportation, refining and utilization, therefore have been a major player in environmental pollution. These activities have to be carried out in such a way as to protect and preserve

the quality of the environment while still achieving desire economic benefits. In Nigeria, this is most pronounced in the Niger Delta area for both upstream and downstream sectors as their operations have rapidly increased. The essence of effluent water treatment is to protect the environment from further environmental degradation (Ademiyi, 2005; Amadi, 2007; Butler and Cartter- Franklin, 2004; Dyer, 2003; Oudijk, 2003; Ritch, 1973; Ubaeze and Egereonu, 2004; Thurman and Heydema, 1991; Ray, 2008; Penchera and Hristozou, 2005; Oyoh and Osoka, 2007 and Kukwa, 2007). The present practice of most companies in wastewater disposal during exploration and production operation, to the receiving; lakes, rivers, ocean and sea without treatment are unacceptable. Consequently, the increase in petroleum and gas production and inadequate treatment implies that the future of man in these regions remains uncertain. Also, considering the current trends in Government environmental regulations regarding the disposal of wastewater (effluent water), there is urgent need to evaluate alternative and acceptable ways of reducing wastewater disposal into the environment (Ukpaka, 2009). Bioremediation treatment techniques are in use to enhance environment clean up of polluted ponds, lakes, rivers, seas and the ocean. Field and laboratory investigations reveal that the treatment technique can be influenced by temperature, pH, dissolved oxygen, biological oxygen demand, chemical oxygen demand, moisture content, solubility of the contaminants etc. (Grandy et al., 1988). Studies conducted in similar environments confirm the influence on the physicochemical properties on the biodegradation process (Arvin, et al., 1991; Polee, 1991). Field and laboratory studies were conducted to assess the performance of functional parameters in hydrocarbon degradation in pond system. The impact of continuous discharge of wastewater on the individual hydrocarbon of pond system was examined. No realistic mathematical model has been developed to monitor and predict the effect of energy, mass and momentum transfer on effective degradation of individual hydrocarbon in pond system. But this paper presented the effect of momentum transfer in conjunction with the mass of wastewater discharged into the pond system. The model was achieved by using non-growth Monod equation which describes the biodegradation of hydrocarbon and was correlated with the principle of force balance model on a fluid element in a pond using all the necessary tools and techniques. 2. The Model 2.1 Models for Competitive Inhibition Relationship of Individual Hydrocarbon Degradation . The non-growth Monod equation describing the biodegradation of petroleum hydrocarbon when present as the sole substrate is
SHC HCe

SK K SX R + = (1)
HCe

where RHce is the degradation rate of petroleum hydrocarbon (effluent when present alone (mgHc/l-d); KHC = maximum specific degradation rate of hydrocarbon (Hc) (g/g vss-d); S = Liquid concentration of hydrocarbon (mg Hc/l). X = biomass concentration (mg Vss/l); KSHC = half saturation concentration of hydrocarbon (mgHc/l). Using the two-compound competitive inhibition equation (Bailey and Ollis 1986):

 ++ =
i SHC HCe HCe

K I SK K SX R 1
(2) where I = liquid concentration of a competing compound (mg/l) and Ki is an inhibition constant (mg/l). However, some researchers have shown that the inhibition effect of a compound can be described by the Ks of the compound (AlvarezCohen and McCarty, 1991; Change and Alvarez-Cohen, 1994), since the Ks represents the relative enzyme affinity. An extension from two-compound competitive inhibition to four compounds for the interactive effect of influent HC on the effluent degradation is RHCem =

++
SHCin in e SHCe HCe e

K S SK KSX 1 (3) Therefore for every individual hydrocarbon the following equation(s) are obtained RC5em =

 ++
C in nCe

S C in CeS CeCe

K S SK KSX
5 5

5 5 55

1
(4) RCnem =

++
SCnin Cnin Cne SCne Cne Cne

K S SK KSX 1 (5) where n = 5,6,7,8,9,10,11 etc. RHCem is the degradation rate individual hydrocarbon in the mixture with other component of petroleum (mg/l-d), Scnin is the liquid concentration of other individual hydrocarbon present in the influent (mg/l), KSCnin is the half saturation concentration (mg/l). Similarly, an extension from two-compound competitive inhibition to eleven compounds for the interaction effect of C6 to C11 on C5 degradation is RC5em=

+++++++
SC in

C in SC in C in SC in C in SC in C in SC in C in SC in C in C e SC e CC

K S K S K S K S K S K S SK KSX
11 11 10 10 9 9 8 8 7 7 6 6 55 55

1
(6) where KSC6in, KSC7in, KSC8in, KSC9in, KSC10in and KSC11in = half-saturation concentration of C6, C7, C8, C9, C10 and C11 respectively (mg/l) Then, combining equations (1) and (7)??? yields
+++++++ =+
11 in 11 in 10 in 10 in 9 in 9 in 8 in 8 in 7 in 7 in

6 in 6 in 55 555

1
SC C SC C SC C SC C SC C SC C C e SC e C SC HCe C em

K S K S K S K S K S K S SK SK R R

(7)
5 5e 6in 7in 8in 9in 10in 11in 555 C e SC C C C C C C C SC HCe C em

SKSSSSSS SK R R +++++++ = + (8)

where KSC6in = KSC7in = KSC8in = KSC9in = KSC10in = KSC11in, equation (7) can be reduced to equations (8), thus RHCe = RCne, therefore equation (8) reduces to:
5 6in 7 in 8in 9in 10 in 11in 55 5 5 SCCCCCCC C SC Ce C em

KSSSSSS SK R R +

= + (9)

where C6in C7in C8in C9in C10in C11in

S S S S S S = C6in C7in C8in C9in C10in C11in S + S + S + S + S + S , total C 6in C 7in C8in C9in C10in C11in S S S S S S
concentration in liquid (mg/l) Then, if SC5 >> KSC5 equation (9) reduces to equation (10);
6in 7 in 8in 9 in 10 in 11in 5 5 5 CCCCCC C Ce C em

SSSSSS S R R (10)
Comparison of mixture: Interaction effects in two compound mixtures of BTPX were reported by Chang et al., (1993) and Oh et al., (1994) as well their research work also developed model equations to describe their experimental findings. Chang et al., (1993) studied the degradation of benzene, toluene and p-xylene by two pure strains of pseudomonas bacteria, B1 and X1, observation of individual compound on the biokinetic test for maximum specific growths rate (m), Ks and yield (mg cells/mg substrate) were measured which showed that pseudomonas B1 could degrade benzene and toluene, but not P-xylene and pseudomonas X1 could degrade toluene and P-xylene but not benzene (B1 appears to use the TOD pathway while X1 appears to use the TOL pathway). In this thesis competitive inhibition was used to model the interactions of the two compounds degraded as growth substrates by each strain of microorganism.
6 6 6 55 max 5 5

1S K S YK SX
i

+ +
S

The competitive inhibition model was developed by using equation (11). where S1 and S2 = liquid concentration of substrates 5 and 6 respectively. Similarly, for several hydrocarbon components degraded as growth substrate by each strain of microorganism is given as follows: for S6 and S7; Deg Rate 5in mix =
67 7 7 6 6 55

max 5 5

1SS K S K S YK SX
ii

++ ++
S

(12) For S6, S7 and S8 Deg Rate 5 in mix =

678 8 8 7 7 6 6 55 max 5 5

1SSS K S K S K S YK SX
iii

+ + + +++ (13) Deg Rate 5 in mix = +++++=

S 11 11 10 10

9 9 8 8 7 7 6 6 55 max 5 5

1
iiiiii

K S K S K S K S K S K S YK SX
S

6 7 8 9 10 11

+ S + S + S + S + S + S (14)

Therefore Deg Rate 5 in mix = + + + + + =

11 11 10 10 9 9 8 8 7 7 6 6 55 max 5 5

1
iiiiii

K S K S K S K S K S
S

K S YK SX

+ + + + + + 6 7 8 9 10 11 S S S S S S (15)
Oh et a;l (1994) studied the interactions of benzene toluene and P-xylene degradation by a pure culture of pseudomonas and a mixed consortium. In this case, toluene degradation alone was modeled by Andrews inhibitory kinetics and benzene degradation was modeled by Monod kinetics. Because the Kinetics of these individual compounds was not described by the same model, the competitive inhibition equations for each were different. In this research work the Andrews inhibitory kinetics approach was applied for the individual hydrocarbon and the competitive inhibition equations for each were different using Andrews inhibitory kinetics technique; thus,

( ) SC C C C total
CC C

KSKS

S
5556 max 5 5

++ = (17) Deg Rate 5 in mix = (11)

5

SCn Cn Cn Cn Cn

( CnCn total )

KSKS

S
1 max

++ = (18)
+

In this model, Kc5C6, KC6C7, KC7C8, KC8C9, KC9C10, CC10,C11 and KC11C12 are an interaction constants. 2.2 The Momentum Model 2.2.1Force Balance Model on a Fluid Element in a Pond The conservation of the momentum equation can be expressed in a linear or angular momentum form. Momentum is defined as a product of mass and its velocity. However, is derived here in the interest to determine the effect of momentum transfer due to continuous discharge of wastewater on biodegradation of petroleum hydrocarbons in an oxidation pond system. Considering the volume element or control volume as shown in Figure 1 Figure 1: Force balance on a fluid element in a pond From Figure 1 the force acting on the fluid element (petroleum hydrocarbons and other components) at length x is express mathematically as: Gravity Fg = o gAxS (19) Friction Ff = f gAxS (20)

Hydrostatic F1 F2 = g y A x
2

( )

(21)

where x = length of fluid element, (m); A = average cross-section area, (m2); Sf = slope of the energy line (m/m); SO = below the surface water slope, (m/m); and y = centroid height of the hydrostatic force, (m). The energy line represents the total head time at each section i.e. Total head = datum + water depth + g V 2 2 , where

g V 2
2

= the velocity head. (22) The energy slope line, the water surface slope and below the water surface slope are assumed not to be the same in this research work. For this investigation it is assumed that the energy line has a slope of S f and below the water surface level has a slope of So. Then, the conservation of momentum equation is given as. = = (23)

dt dU
= Fg + (F1-F2) - Ff (24) Substituting equations (19, 20 and 21) into equation (24) yields

()(

of

y A gA xS

x U gA xS dt d = + 2 2 1 (25) Since ( )
+ = x u V t u Ax dt dU

(26)

Therefore, substituting equation (26) into equation (25) and rearranging the equation obtained yields

( ) ( y A)
X gA X S S g x du V t u A X of
2 2 1

= + + (27)

Since the investigation will be conducted under the following conditions, a constant cross-section and onedimensional flow, thus equation (27) becomes

The rate of change of momentum for the volume The resultant of the forces acting on the volume
FF S SF y F y
below the surface Energy slope water

12

( ) gSS
of

x u V t u=

 + (28) 2.2.2 Mathematical Application for wet season momentum transfer in pond system
Recalling equation (28)

()

II o f

gSS

x u V t u= +
Equation (28) is expressed by considering the following boundary condition, such as, at X11 = 0, t = 0, U = C11 at X11 = L, t = T (29) Equation (28) can be expressed using mathematical tools, thus U = T X (30) Equation (30) can be resolved using separation of variable method as well as applying the necessary boundary conditions; we have the following expression as stated from equation (31) to (41) (a) T11 = C e t 2
3

(31)

(b) x
11 11 2

11 =

4 x V

Ce

(32) (c) C3 =

C Cn (33)
4

(d)

()
II of

V gSS 2 = (34)

(e)

t L V II II = (35)
(f) UL(11) =

()()

II of II II II of

V gSSL V L V gSS

CeCe
11

3 4 (36)

(g) UL(11) =

()()



II of II II of

V gSSL L V gSS

eCe C C
n
11 2

4 4

(37) (h) UL(11) =

()()

II of II II of

V gSSL L V gSS n
11 2

Cee

(38)

(i)
2n

()

L II

U C In 1 II II
II

LV V = (39)
(j) So sf =
n 2

()

L II

U C In 1 II II
II

LV V (40)
(k)
Ln 2

()

U Cn In 1 o f II
II

gSSL V V=
II

(41) Where C3, C4 and Cn are constant, X11, is distance (m), V11 is velocity (m/day), UL (11) is momentum (mol%) (m/day), is constant, g is acceleration due to gravity (m/s2), t is time (day). The developed model in equation (41) can be applied in monitoring the rate of degradation of the individual hydrocarbon, estimating the degree of influence of momentum transfer due to continuous discharge of wastewater and the affected area, estimating the spreading rate and diffusion rate for each hydrocarbon component in the oxidation pond system upon the influence on internal fluid friction, as each horizontal layer of fluid shears over the next layer, producing a shear loss where Sf 0. The use of this equation (41) is useful for the prediction as well as correlation of velocity and substrate concentration as a function of distance and time upon the influence of

internal fluid friction for wet season. 2.3Model for Correlation of Momentum Transfer with Competitive Inhibition Relationship of Individual Hydrocarbon Degradation for wet Season Recalling equation (1) and rearranging the equation yields
HCe HCe HCe SHC

KR RK S =
Assuming that Cn = S concentration at the discharge point (receiving point). Therefore equation (1) can be writer as Cn =
HCe HCe HCe SHC

KXR RK
Therefore, substituting equation (1) into equation (38) yields
()

()

HCe II L

II
II II ofL

TX gSS HCe HCe HCe SHC

KXR RK l (42)

But, using the two-compound competitive inhibition equation yields

()

HCe II L

()

II
II II of II

L TX gSS L HCe HCe I HCe SHC

KXR K RKI ll 1
(43) Similarly, the momentum transfer relationship for an extension from two-compound competitive inhibition to four compounds for the interactive effect of influent on the effluent degradation is given mathematically as:
()

()()

HCem II L



II II of II II of

L V gSS L V gSS HCem HCem SHCin in HCem SHC

KXR K RKS ll
2

1
(44) Therefore for every individual hydrocarbon the following equations are obtained

()()

 + =

II II of II II of

L V gSS L V gSS C e C em SC in in C e SC e LC em II

KXR

K S RK Ull
2

55 5 55 5

1
(45)
()()

 + =

II II of II II of

L V gSS L V gSS C e C em SC in in C e SC e LC emII

KXR

K S RK Ull
2

66 6 66 6

1
(46)
()()

 + =

II II of II II of

L V gSS L V gSS Cne Cnem SCnin in Cne SCne LCnem II

KXR

K S RK Ull
2

1 (47) Similarly equation (47) can be written as;

()
II II

()

o f II

gSSL V V = 2
n LCnem II

C U In (48)

where Cn =
Cne Cnem SCnin Cnin Cnem SCne

KXR K S RK 1+
Similarly, equation (48) can be written as
()
II II

()

o f II

gSSL V V = n
LCnem II 2

C U In 1
(49) The mathematical equation obtained in equation (48) is found useful in monitoring, predicting and simulating the degradation and microbial growth rate kinetics on the characteristics of different in wastewater (influent) discharged and its momentum transfer on the individual hydrocarbon concentration. Equation (48) can be applied in the study of the kinetics of biodegradation and the characterization of the product inhibition due to momentum transfer in the oxidation pond system. Equation (49) can also be expressed in terms of depth and time. 2.4 Experimental Approach

The primary objectives of this study, is to identify and map out potential suitable approach for bioremediation of polluted ponds for continuous discharged and as well as effect of momentum transfer due to continuous discharge of wastewater in biodegradation process. In order to have a better understanding of effect of momentum transfer on biodegradation of contaminants, investigation was conducted on contaminants distribution in surface, subsurface and as well with time. As mentioned earlier the investigation is aimed to determine the following: (a) to determine the effect of momentum transfer on biodegradation of individual petroleum hydrocarbon contaminant, (b) to recommend the best period of carrying out bioremediation process on site ( wet season), (c) to recommend the best approach of carrying out bioremediation process in oxidation pond system either by continuous discharged of wastewater or batchwise method of wastewater treatment, (d) provide suitable design for bioremediation in an oxidation pond process; (e) to recommend the best bioremediation programme. 2.4.1Equipment and Material The equipment and material which shall be used for the experiment are as follows: pH meter, Burette, Special automatic pipette, Sample bottle, Platinum crucible, Water bath, Beaker 250ml, Detector (infrared detector), Thermometer, Gas chromatography. Materials: for the materials we have buffer solution (pH7 and pH4), effluent samples, manganese II chloride (mncl2), 8.00g of Mgcl2.4H2O with be dissolved into 1litre of distilled water, 85% of phosphoric acid, precipitating reagents, Iodometric determination on titration, sodium thiosulphate (Na2S32O3), 0.01N, 2.4829 of Na2S2O3.5H2 will be dissolved in 1liter of distilled water, Zinc iodine starch solution, Ammonia/Ammonium chloride (NH 3/NH4cl) buffer solution, EDIA solution, sodium hydroxide, enviochrome T-black indicator, muroxide indicator and sulphuric acid. 2.4.2Sampling Samples were carried out at specific points in the pond using automatic pipette, attached on a slide rule to determine the various depths and the wastewater samples were collected in one of the oxidation pond in Niger Delta area of Nigeria, at various sampling point in the oxidation pond system. The collected samples were transfer into sample bottles and store in cool container before transfer to the laboratory for analysis. Similarly, samples were collected at various distance (surface). where, o is hydrocarbon, is particle, is wave formation created as a result of disturbance (continuous discharge of wastewater into the pond, direction of flow A0, A1, A2, A3, A4, B0,B1, B2, B3, B4, C0, C1, C2, C3, and C4 are sampling points Figure .2: The main experimental investigation on the force acting on the immersed object-surface floater along side with the fluid element in a pond system (for continuous discharged of wastewater) 3. Results and Discussion The experimental investigation was carried out to determine the effect of momentum transfer on competitive inhibition of hydrocarbon degradation in pond system for wet season and the results obtained from the research are presented in Figures and Tables as shown in this paper. Modeling the effect of momentum transfer on competitive inhibition of hydrocarbon in pond system was

investigated for wet season. The degradation pattern of this system is slightly different as most of the hydrocarbon concentration decreased with increase in distance and time. From Figure 3, it is seen that the rate of change in substrate concentration decreases with increase in distance and time for wet season momentum transfer due to continuous discharge of wastewater in pond system. The result presented in Figure 3 showed decrease in wet season substrate concentration of the following i-C5, n-C5, C6and C7 with increase in distance and time.
Figure 3: Wet season substrate concentration at surface versus distance and time
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 10 20 30 40 50 60 distance (m)

i-C5 n-C5 C6 C7 0 4 8 12 16
Hydrocarbon concentration (mol %) (m/day)

time (week)

. oooooooooooo ooooooo ooooooo ooooooo ooooooo ooooooo ooooooo ooo o o o o o o o o o o oo. . . . . . .. .

. . ..... .... ... ... . ...... AAAAA BBBBB

Samplin g point

CCCCC
Immersed object in water Soil Soil Soil Surface land Surface land Discharged pointed

From the result of the analysis, it is seen that the C8, C9, C10 and C11 concentration decreases with increase in distance and time for wet season momentum transfer. The variation on the individual hydrocarbon (C8, C9, C10 and C11) concentration can be attributed to the variation in distance, time as well as momentum transfer due to continuous discharge of wastewater as shown in Figure 4. The rate of momentum of individual substrate decreases with increase in distance; this can be attributed to variation in the rate of momentum of individual substrate with variation in distance presented in Figure (5). Other functional

parameters that can influence the individual hydrocarbon degradation of a pond system under going bioremediation includes microbial activities, opposing velocity, mass of individual hydrocarbon, wind velocity, continues discharge of waste water into the receiving pond, human factors, physiochemical factors etc. 4. Conclusion The above study brings out the following conclusion on the effect of momentum on the competitive inhibition of hydrocarbon degradation in pond system for wet season. a. The effect of momentum transfer resulted to the retardation of the microbial growth rate in pond system for the various microorganisms identified and isolated from the system for wet season as presented in appendix I (Table 1) b.The effect of momentum transfer on the physicochemical parameters reduces the degradation rate of the individual hydrocarbon as well as the microbial growth rate in pond system for wet season. c. The momentum influence the lag, progressive, stationary and decline phase of the pond system. d.Monitoring and predicting the effect of the physicochemical parameters in pond system upon the influence of momentum transfer for continues discharge of wastewater is a major contributor to competitive inhibition of individual hydrocarbon degradation in pond system. These can be attributed to the toxic nature of the pond system and bonding characteristics of
Figure 5: Wet season rate of momentum transfer of substrate concentration versusd istance 0.00E+00 5.00E-06 1.00E-05 1.50E-05 2.00E-05 2.50E-05 3.00E-05 3.50E-05 0 5 10 15 20 25 distance (m)
UC6EM(N) UC7EM(N) UC8EM(N)

Rate of momentum transfer of substrate (mol %) (m/day)

Figure 4 :Wet season substrate concentration at surface versus distance and time 0 2 4 6 8 10 12 14 0 10 20 30 40 50 60 distance (m) C8 C9 C10 C11 0 4 8 12 16 time (week)
Hydrocarbon concentration (mol %) (m/day)

the substrate increases thereby reducing the effect of momentum on the rate of flow and diffusion of the individual hydrocarbon degradation, as presented in appendix II (Table 2). '";no/ledgments We hereby acknowledge the support of Total E & P Nigeria Ltd, and Jospaka Ventures Nig Ltd for their support during the research period as well as the Department of Chemical /Petrochemical Engineering and Microbiology Department of

RSUST Port Harcourt for using their Laboratory for carrying out the investigation. Appendix I Table 1: Microbial population sampled in the pond system for wet season Time (week) Sampling point (m) Microbial population (cfu/ml) E, Coil Enterococoi organisms Pseudomonas Sp. Bacillus 0 4 8 12 16 0 10 22 37 53 2.3 x 104 4.4 x 105 1.3 x 107 0.9 x 107 2.0 x 108 3.0 x 104 6.3 x 105 2.2 x 106 1.1 x 107 4.7 x 108 3.3 x 103 5.1 x 107 3.6 x 106 1.7 x 108 7.0 x 108 1.5 x 103 2.8 x 105 1.5 x 105 3.7 x 106 2.7 x 105 Appendix II Table 2 Experimental determination of mean physiochemical properties of wastewater upon the influence of momentum transfer in pond system with specified distance of 0, 10, 22,37and 53 m. Parameter Unit Concentration of the parameters Sampling point Week 2 Week 4 Week 6 Week 8 Week 10 Week

12 Week 14 Week 16 pH at recorded temp. 7.21 6.40 7.00 6.88 6.73 6.95 7.38 6.74 Measured temp of pH oC 27.4 26.0 26.8 27.0 26.5 26.9 26.3 26.5 Turbidity NTu 27 20 24 22 28 17 19 26 Conductivity mS/cm 10.8 10.7 11.0 11.3 10.5 10.9 10.3 11.0 Alkalinity/Bicarbonat e mg/l 51.1 60.7 52.0 42.6 33.0 69.5 70.0 374 Total suspended solid mg/l 40.5 45.1 57.9 53.1 46.0 41.4 56.8 60.3 Total dissolved solids mg/l 7.14 7.73 7.25 6.81 6.30 6.71 7.33 7.46 BOD (biochemical oxygen demand) mg/l 10.10 18.2 6.9 23.7 28.0 14.6 12.0 16.2 COD (Chemical oxygen demand) mg/l 44.8 53.0 36.3 40.1 47.0 31.8 50.9 61.5 Salinity (as chloride) mg/l 9,271 8,118 7004 10,513 11,646 10,715 11,833 10,731 Iron mg/l 0.49 0.51 0.33 0.27 0.41 0.21 0.25 0.30 Nitrate mg/l 5.1 3.8 3.5 2.6 1.8 2.9 2.0 1.7 Sulphate mg/l 1,837 1,600 1,648 1,517 1,225 1,439 1,500 1,771 DO (Dissolved oxygen) mg/l 3.55 4.01 3.85 2.77 3.00 2.80 3.41 3.82 Reference Ademiyi,, O.D. (2005), Evaluation and modeling of effluent from electroplating plant. Journal of Modeling, Simulation and Control (AMSE), 66 (4) : 23-38. Amadi, S.A; Ukpaka, C.P. and Jacob, N.N. (2007), Mechanism of the microbial corrosion of Aluminum Alloys. Journal of Industrial Pollution Control, 23 (2) : 197-200, Arvin, E. Jensen B.K. and Gundersen, A.T. (1991), Biodegradation Kinectics of Phenols in an aerobic biofilm at low concentrations. Water Science and Technology, 23, (7) : 1375-1384, Butler, A and carter-Franklin, J.N (2004). The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products. Natural Products Report,. 21, 180-188, Dyer, M. (2003). Field investigation into the biodegradation of TcE and BTEX at a formal mental plating work, Engineering Geology, 70 (3-4) : 321-329, Grandy A.F. and Grandy, E.T. (1988).Element of Bio-environmental Engineering, Engineering Press Inc. San Jose Calif, 33, 333-338, Kukwa, D.T. (2007).Industrial potentials of RUTSU Rivers water in Sankera, Ukum, International Journal of Physical Science, 1 (1) : 38-44, Oudijk, G. (2003), Estimating the minimum age of a chlorinated solvent plume in groundwater with chlorofluoro carbon (CFC) and tritium methodologies, Environmental Forensics, 4 (1) : 81-88, Oyoh, K.B and Osoko, E.C. (2007). Rate model for bioremediation based on total Hydrocarbon content. Journal of the Nigeria Society of Chemical Engineers, 22 (1&2) : 50-56, Pencheva T and Hristozou, I. (2005), Modeling of waste water treatment process in the class of distributed parameters

objects; Journal of Modeling, Simulation and Control (AMSE), 66 (3) : 72-78, Polec, B. (1991), Influence of Fermenter Inoculation and temperature on efficiency of impurity removal from sugar factory wastewater and biogas production, Gazeta Cukrownikzai, 99, (1) : 17-20, Ray, N. (2008), crude oil pollution and the implication for Agriculture in Egbema Clan. The Nigerian Academic Forum A multidisciplinary Journal, 15 (2) :17-23 Riggs, L.G. (1973), Environmental Systems Engineering. McGraw-Hill Book Company, New York. 116- 128. Thurman N.P and M. Heydema, (1991). A Microbial approach to cleaning used oil-based drilling mud, SPE230061, 291293, Ubaezue U. and Egereonu. K.I. (2004), Investigation on nitrate pollution and groundwater of Owerri and environs, South Easter Nigeria. Journal of Modeling, Simulation and Control (AMSE), 65 (1) : 59-76, Ukpaka, C.P. (2009), Development of models for the prediction of functional parameters for hydrocarbon degradation in pond system, Ph.D Thesis, Rivers State university of Science and technology Port Harcourt, 85-120.

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P-14 PETROCHEMICAL DEVELOPMENT IN NIGERIA:

The Need for Pilot Plants

Godwin J. Igwe
Center for Gas, Refining & Petrochemicals (CGRP) Institute of Petroleum Studies (IPS), University of Port Harcourt, Rivers State, Nigeria www.cgrpng.org; www.profigwe.com

ABSTRACT
Pilot plants are used for developing concepts, research, demonstration, testing of process and products. Installing pilot plants will help the country to 1) fully use the services of these plants to support and improve the operations of the refineries; 2) save foreign exchange in such services currently done abroad; 3) contribute to the Nigerian Content programme of the Federal Government; 4) contribute to research and development in the downstream sector; 5) contribute to human capital development in the oil and gas sector. All these could be achieved through a deliberate strategy to build, operate, commission a pilot refinery in Nigeria, to train, grow the refining and petrochemical industry as the sure path to diversifying the countrys revenue stream, and growth in other sectors. Keywords: Pilot plants, Feedstock, Refining, Petrochemicals, Hydrocarbon Value Chain 1.0 INTRODUCTION Africa, and specifically, Nigeria, faces significant developmental challenges, key among which is an undiversified production structure. Processing and transformation of their raw materials to marketable

products instead of commodity trading (selling the crude oil and natural gas and sharing the money) should deliberately focus on value creation to actualize industrialization and reduce unemployment in the extractive industries. By capitalizing on the commodity boom to ensure domestic economic spillovers in the form of well-paid jobs that seek to move into value-addition activities, Nigeria will benefit substantially if its higher education institutions produced more of these demanded skills. The lack of skills for the extractive industries prevents African countries from provision of local content that generates domestic economic spillovers (World Bank, 2013). Nigeria, as a major oil producer cannot continue to import refined petroleum products. The gap is that we cannot service the refineries to full capacity without our Research and Development (R&D) having Pilot plants. Pilot plant testing is the essence of Research and Development, and it is unavoidable as a teaching, research, and manufacturing tool. It is like an aeroplane pilot not having practiced in a flight simulator, or a medical doctor not having touched a patient. The Task Force set up by the Federal Government of Nigeria, on refineries, summarized their findings (National Refineries Special Task Force Report, 2012) as follows: There are 42 refineries in Africa. Nigeria has 3 and the third largest combined capacity of 445,000 bbl/d. The countries with higher number and capacity are South Africa and Egypt, with 2 and 9 refineries respectively, and corresponding capacities of 545,000 and 774,900 BPD respectively. Nigerian refineries have the worst performance record among the 42 refineries, with an average capacity utilisation of only 18%, compared to 81% and 85% respectively for Egypt and South Africa in 2006-2009.
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One may objectively be inclined to interpret the findings of the Task Force to mean that growing our refining and petrochemical industries can be achieved, through a deliberate strategy to build, operate, commission a pilot refinery in Nigeria, to train the required manpower as the sure path to diversifying the countrys revenue stream, and growth in other sectors. This is because capacity building is a prerequisite for economic development. This paper, therefore, seeks to discuss generally, pilot plants, oil and gas value chain with respect to petrochemicals development in Nigeria. The value of bridging the gap in training using pilot plant is expected to ignite sustained economic growth and competitiveness in science and technology capacity industry-related research to increase technology absorption, raise total factor productivity, and generate new competitive sectors.

1.2 HYDROCARBON PROCESSING It all starts with processing hydrocarbons in the oil patch. The processing steps are selfexplanatory as shown in Fig.1. FIGURE 1: PROCESSING HYDROCARBONS IN THE OIL PATCH 2.0 THE OIL AND GAS VALUE CHAIN 2.1 UPSTREAM Fig. 2.1 depicts activities related to winning of crude oil and gas, drilling and operation of oil and gas producing wells, construction and operation of oil and gas gathering, separation and treatment facilities and transportation of personnel and equipment to and from upstream petroleum locations. FIGURE 2.1: UPSTREAM ACTIVITES
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2.2 MIDSTREAM Fig. 2.2 shows construction and operation of crude oil and gas transport pipelines, oil refineries and gas processing facilities, oil and gas storage facilities and coastal or ocean going tankers, rail cars and trucks for transporting and marketing petroleum products on wholesale basis. FIGURE 2.2: REFINING IN MIDSTREAM 2.3 DOWNSTREAM Fig. 2.3 involves construction and operation of pipelines for distributing and marketing petroleum products and gas to small customers, storage tank farm for petroleum products and city gate reception terminals for gas distribution and the sale, marketing and retailing of petroleum and gas products. Also touches consumers through thousands of products such as fuels (gasoline, diesel, jet fuel, heating oil) and non-fuels (asphalt, lubricants and non synthetic rubber, plastics, fertilizers, antifreeze, pesticides, pharmaceuticals) FIGURE 2.3: PETROLEUM DISTRIBUTION IN DOWNSTREAM 3.0 OIL AND GAS HYDROCARBON STRUCTURES To understand how unrefined oil and unprocessed gas are converted into useful products, it is necessary to be familiar with four types of hydrocarbons: Paraffins Olefins Naphthenes, and Aromatics
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All of these compounds are arrangements of carbon and hydrogen atoms, and sometimes they include other elements such as oxygen, sulfur, and trace metals.

3.1 PARAFFINS FIGURE 3.1: STRUCTURE OF PARAFFIN HYDROCARBONS Natural gas and a substantial portion of crude oil are composed of paraffin hydrocarbons. The simplest is methane, the main ingredient of natural gas. It has one carbon atom attached to four hydrogen atoms. Examples are ethane and propane, also components of natural gas. Each carbon atom can bond or attach to four other atoms and each hydrogen atom can bond with one other atom. They are saturated hydrocarbons because paraffins have the greatest possible number of hydrocarbons. 3.2 OLEFINS FIGURE 3.2: STRUCTURE OF OLEFINS HYDROCARBONS Like paraffins, olefins are chains of carbon atoms with attached hydrogen atoms. However, olefin chains do not have the greatest possible number of hydrogen atoms.
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If two hydrogen atoms are missing, two carbon atoms in the chain will form a double bond to make up for the deficiency. An example is ethylene, an important petrochemical. Olefins are known as unsaturated hydrocarbons because of their hydrogen deficiency. They do not occur naturally in crude oil but are formed in the refinery by the breakdown of larger hydrocarbon molecules. Olefins are very useful in creating certain refinery products and petrochemicals. 3.3 NAPHTHENES FIGURE 3.3: STRUCTURE OF NAPHTHENES HYDROCARBONS The carbon atoms of naphthenes form rings rather than chains, so naphthenes are called ring compounds or cycloparaffins. Hydrocarbons in this group have names that begin with the prefix cyclo to indicate ring structure. Example is cyclohexane, a hydrocarbon often occurring in natural gasoline. The carbon rings of naphthenes are saturated with hydrogen atoms. 3.4 AROMATICS
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FIGURE 3.4: STRUCTURE OF AROMATICS HYDROCARBONS Aromatic hydrocarbons are compounds that contain a ring of six carbon atoms with alternating double bond and single bonds and six attached hydrogen atoms. The most important type of structure is known as a benzene ring. The most important aromatics in refinery production are the BTXs Benzene, Toluene, and Xylene. Aromatics occur naturally in crude oil. They are also created by refinery and petrochemical plant processes. 3.5 Other Elements

Anywhere from 2 to 50 percent of a crude oil may be composed of compounds containing oxygen, nitrogen, sulfur, and metals. Oxygen content can be as high as 2 per cent, and nitrogen content as high as 0.8 percent. Sulfur content ranges from traces to more than 5 percent. If a crude contains appreciable quantities of sulfur or sulfur compounds, it is called sour crude; if it contains little or no sulfur it is called a sweet crude. Trace metals contained in crude oil include sodium, magnesium, calcium, strontium, copper, silver, gold, aluminum, tin, lead, vanadium, chromium, manganese, iron, cobalt, nickel, platinum, uranium, boron, silicon, and phosphorus. Of these metals, nickel and vanadium occur in the greatest quantities. 4.0 Pilot Plants for Research & Development In order to fully contribute to the development of oil and gas downstream, an opportunity to accelerate the technical support to refineries operations and performance through the use of pilot plants has been identified (Fig.4.1). Consequently NNPC R&D and Institute of Petroleum Studies (IPS) are collaborating to further the realization of the acquisition, installation and operation of pilot plants as means to add value to the current efforts at imparting positively on lives. 4.1 Technical and Economic Considerations The refineries in Port Harcourt, Warri and Kaduna have remained the only assets producing light to heavy distillates for local consumption and export. The refineries have a combined installed capacity of 445,000 bpd. A comprehensive network of pipelines and depots strategically located throughout Nigeria links these refineries. These refineries have been operating over the years and there is no domestic pilot plant service for them. Existing methods of solving problems may differ from the management of each of the plants. Process technology and specific equipment problems are expected to be solved by the licensors after reports of troubleshooting, while other less complicated technical and operational problems are solved by experts (both local and from overseas) advice and/or other methods. Test runs for different objectives are sometimes undertaken by the management of these plants: program is developed and implemented with performance monitoring. In other cases specialized studies and modeling are done using appropriate engineering softwares, e.g., ASPEN Engineering Suite, etc. In spite of all these, pilot plants provide a middle stage data and process conditions between

engineering software predictive evaluation and the implementation in a commercial plant. It is this vacuum that is to be filled by this initiative, which is designed to acquire and install pilot plants to provide full support for the refineries. In general, refineries require full technical support in the following broad areas: (i) Laboratory and technical services (ii) Engineering services (especially using ASPEN Engineering Suites, etc) for performance evaluation, predictive studies and comprehensive site or specific process units/equipment studies,
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(iii) Pilot plants support for problem solving, testing of feedstock, intermediates, new and/or equilibrium catalysts performance evaluation, etc. (iv) Items (i) and (ii) are currently provided locally within the refineries and outside (including NNPC R&D, Port Harcourt) to a large extent, but item (iii) is totally absent locally. Studies requiring pilot plants are mostly done abroad or solutions derived from results in item (ii). 4.2 Objectives of the programme The areas identified for use of the pilot include proofing on-going research concepts, testing results and scale-up activities. Consequently the objectives (Igwe, 2012) of acquiring pilot plants (Igwe, 1989, 2013) will be: (i) Testing results of available studies in NNPC R&D and elsewhere as applicable to prove concepts, techniques and solution, (ii) Studying processes and problems of existing NNPC downstream facilities, (iii) Scale-up of laboratory bench analysis and procedures, (iv) Teaching and demonstration 4.3 Technical Considerations Pilot plants are used for developing concepts, research, demonstration, testing of process and products. Pre-built modular process plants may be appropriate to replace or augment existing facilities where space is an important consideration. Scale-up and process development at a larger-than-pilot scale, requires process and product demonstration plants. Skid-mounted and modular, demonstration plants can generate significant quantities of product for market testing, and are often used together with pilot plants to support the ongoing operation and optimization of commercial-scale units. Considering the varied processes, technologies and systems, flexible and modular pilot plants will be appropriate. For less complex and lower capacities, pilot plants allows the operators flexibility in

managing applications to existing configurations; but for higher capacities and complexities, it may not make economic sense. Flexibility in process flowsheet configuration for pilot plants, especially for small capacities and less complex units allows for opportunities to study and accommodate varied process configurations. These can enable the operators to adapt various flowsheet and process conditions to match the desired flow directions and plant configurations, e.g., hydrotreating and dehydrogenation can be accomplished by a flexible pilot plant, and will meet the above stated objectives. The scope will focus on the following three areas: (i) Feedstock (crude oil) preparation atmospheric and vacuum distillation (Crude distillation unit (CDU) and Vacuum distillation unit (VDU)), (ii) Catalytic conversion (Catalytic reforming unit (CRU), Hydrotreating units for naphtha and kerosene), (iii) Products refining/purification (Fluid catalytic cracking FCC). These process units are at the centre of refining in terms of quantity and quality of light to heavy distillate fractions. Targeting to improve these plants will impact remarkably on the overall performance of the refineries. 4.4 Benefits of the Programme Installing pilot plants will help the country to: (i) Fully use the services of these plants to support and improve the operations of the refineries, (ii) Save foreign exchange in such services currently done abroad, (iii) Contribute to the Nigerian Content programme of the Federal Government, (iv) Contribute to research and development in the downstream sector, (v) Contribute to human capital development in the oil and gas sector
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FIGURE 4.1: FIGURE OF A TYPICAL PILOT PLANT FIGURE 4.2: PREFABRICATED MODULES Fig. 4.2 is an example of pre-fabricated modules. This project offers us the opportunity to produce petroleum products for teaching and research purposes. The project should be perceived as a challenge to advance Nigerias interest in capacity building, thereby improving the economy, hence providing better life for our next generation. 4.5 Methodology of the proposed study Crude oil and natural gas will be provided by the Nigerian National Petroleum Corporation. Modeling and Simulation softwares will be provided by GSE EnVision of Madison, NJ. USA. At least, two out of the 6 (Six) Pilot Plant units below, will immediately be needed for capacity building and training. Saudi R & D (Saudi Petrochemical Sector R&D News & Report 2009) has 8 (eight) pilot plants.

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a) Desalter Washes out salt from the crude oil before it enters the atmospheric distillation unit. b) an atmospheric distillation Distills crude oil into fractions. c) a naphtha hydrotreater Unit uses hydrogen to desulfurize naphtha from atmospheric distillation. Must hydrotreat the naphtha before sending to a Catalytic Reformer unit. d) a catalytic reformer unit is used to convert the naphtha-boiling molecules into higher octane reformate (reformer product). An important byproduct of a reformer is hydrogen released during the catalyst reaction. The hydrogen is used either in the hydrotreater or the hydrocracker. e) a SRGO (Straight run gas oils) hydrotreater A distillate hydrotreater unit desulfurizes distillates (such as diesel) after atmospheric distillation. f) and a visbreaker unit. A visbreaking unit upgrades heavy residual oils by thermally cracking them into lighter, more valuable reduced viscosity products. Fig. 4.3 shows some feedstocks and building blocks for petrochemical molecules. Fig. 4.4 is a process flow sheet in a heavy liquid cracker. How to link potential hydrocarbon value chain options, and processes, to grow our refining and petrochemical industries, is schematically shown in Fig. 4.5. FIGURE 4.3: PETROCHEMICAL FEEDSTOCKS & BUILDING BLOCKS
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FIGURE 4.4: FLOWS IN A HEAVY LIQUID CRACKER FIGURE 4.5: POTENTIAL HYDROCARBON VALUE CHAIN OPTIONS 5.0 CONCLUSION Many natural resource rich countries are diversifying and transforming their economies using the hydrocarbon value chain for wealth creation. In Nigeria, diversification should involve diversifying the energy mix (from oil to gas) and from fuels to non-fuels as shown in Fig.4.5. The keys to successful transformation of our R&D efforts lie in four strategies, namely: 1) Pilot plant testing. It is the essence of Research and Development, and it is unavoidable as a teaching, research, and manufacturing tool.
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2) Pilot plants provide a middle stage data and process conditions between engineering software predictive evaluation, and implementation in a commercial plant. It is this vacuum that is to be filled by this initiative, which is designed to acquire and install pilot plants to provide full support for the refineries. 3) By capitalizing on the commodity boom to ensure domestic economic spillovers in the form of well-paid jobs that seek to move into value-addition activities, Nigeria will benefit substantially if its higher education institutions produced more of these demanded skills. The lack of skills for the extractive industries prevents African countries from provision of local content that generates domestic economic spillovers. 4) An integrated approach to implementing the identified strategies is vital for the expected capacity building and wealth creation to be realised. Acknowledgements:

The author gratefully acknowledge the most kind, timely, and generous support from NNPC Research and Development Division, and Corporate Planning and Strategy. REFERENCES Igwe, G.J., Uniport/IPS/PTDF 1st International Conference on Petroleum Refining & Petrochemicals, August 27-30th, 2012, p.4 Igwe, G.J., Uniport/IPS/Indorama 2nd International Conference on Petroleum Refining & Petrochemicals, August 28-29th August, 2013, p.10 Igwe, G.J.I., Instrumentation and Maintenance of Equipment in Small and Medium Scale Process Industries, in Third World Countries. Report and Presentation to World Bank Economic Development Institute, Washington, D.C., August 1989. National Refineries Special Task Force Report to the Hon. Minister of Petroleum Resources, August 1, 2012. Saudi Aramco News, 25 January, 2009. http://www.aramcoexpats.com/articles/2009/01/minirefineriesa-catalyst-for-success: Saudi Petrochemical Sector, Research Department Sector Reports, July 2011. World Bank Report No.77422-AFR. Africa Centers of Excellence May 13, 2013. P1(4 #imulation and Performan"e 'nalysis of Propylene 1

Propane #plitter in Petroleum 6efinery Case #tudy

> 2 Bmo1and : ; @assey% 10epartment of +hemical and ?etroleum :ngineering, BniGersity of Byo, Byo, ;igeria%0epartment of +hemicalE?etrochemical :ngineering, >D/a <bom 5tate BniGersity, <Dot >Dpaden, ;igeria 'bstra"t <n this paper the simulation and analysis of an e3isting propyleneFpropane distillation column /ith 1#$ trays /ere carried out- >fter the simulation it /as possible to study and GisualiKe the effect of the Dey Gariables on the distillate composition and reboiler energy reJuirement by means of response surface plots- @y gaining understanding about the influence of the Garious parameters it /as possible to optimiKe the operation of the unit- 6hus for a feed rate of 1%-*&tEh of propyleneFpropane mi3ture, the result of this /orD sho/ed a product yield of (#7 propylene in the distillate from a minimum of (&7 yield- 6he operating parameters /ere increase in column pressure from 1) atm to

%$-% atm, reduced reflu3 ratio from 1$-% to 1$-$% and a lo/er reboiler duty of "-$)31$' DcalEh from "-#31$' DcalEh- Arom these results, it /as eGident that optimum parameters had been established for better control of the splitter column case study /ith the potential of achieGing higher product Juality and improGed energy consumptionIN&6OD5C&ION ?ropylene is one of the most important intermediate petrochemical products1Ger the years, it has maintained a remarDable gro/th in the marDet on account of increasing demand for polypropylene /hich absorbs more than '$7 of all the propylene produced /orld/ide (,eiaritKF>drain and IenKel, %$$))- 1ther important propylene deriGatiGes include acrylic acid, acrylonitrile, cumene, phenol, gasoline blend, trimmers and tetramers for detergents0istillation is probably in the most /idely used separation process in the chemical and allied industries- 6he e3ploitation of Golatility differences is so effectiGe in distillation that the first response of an engineer confronted /ith a separation problem is to search for boiling point differences- <n a typical process plant, distillation process consumes as much as &$7 of the total energy used (2artin et al, 1()1)- Aor many years, the standard operating philosophy for distillation process /as to ma3imiKe reflu3 for ma3imum separation- Ihen energy /as ine3pensiGe, this philosophy held s/ay,o/eGer, /ith increased emphasis on energy efficiency to reduce operation cost as /ell as green house emissions there is an increased tendency to lo/er reflu3 ratio,agger (%$$)) adds that as crude oil and energy prices rise, energy efficiency, together /ith optimiKing product Juality and ma3imiKing high^Galue product yields haGe become more important- 6he obLect of this /orD /as therefore to e3plore the possibility of establishing optimum operating parameters for better control of the process for realiKing higher product Juality and improGed energy consumption&<EO6I Distillation Models 6he separation of liJuid mi3tures by distillation depends on differences in Golatility bet/een the components- 0istillation inGolGes a counterFcurrent flo/ of Gapour up the column and liJuid do/n the column- 6he tray proGides contact bet/een the

reflu3 from the condenser and Gapour from the reboiler, stripping the more Golatile component from the liJuid6he choice of thermodynamic and physical models is an important first step in the design and simulation of a distillation process since this determines the Juality of results obtained (,ill and Mustice, %$11)- <t is therefore necessary to highlight some of the more common models often encountered in practice- 6hese models are found in most easily aGailable te3ts and handbooDs in +hemical :ngineering (e-g ?erry et al-, %$$)h 5innot et al-, %$$))Number of &rays 6he minimum number of tray can be estimated by applying AensDe eJuationH (1) /here is the mole fraction of more Golatile or light Dey, mole fraction of less Golatiles or heaGy Dey, ,a' is the aGerage relatiGe Golatility of light Dey /ith respect to heaGy Dey- 6he subscribes 0 and @ denoteh at the distillate and bottom6he relatiGe Golatility is giGen by eJuation (%) (%) 6he N Galues are taDen from charts by calculating for the bubble point in eJuation (&) and de/ point in eJuation (#) F F F F (&) F F F F (#) 6he number of trays can be JuicDly estimated by ;=%-#;m or more accurately by reading this Galue of ;mE; at the intercept of 4E(4+1) and 4mE(4m+1) from :rbar F 2addo3 correlation!eed Point Bsing eJuation ('), the feed point can be estimated as follo/sH (') /here F number of stages aboGe the feed, including partial condenser, F the number of stages belo/ the feed, including the reboiler- 6herefore (") /here ; is the number of trays in the distillation column6eflu? 6atio 6he reflu3 ratio is the ratio of the flo/ returned as condensed liJuid to the column to the flo/ of top product taDen off- 6he Bnder/ood eJuation (() is used to obtain the minimum reflu3 ratio by solGing for the Galue of /hich lies bet/een the relatiGe Golatilities of heaGy Dey and light Dey using eJuation ())

()) /here is the mole fraction of component in feed, is the thermal condition of feed(() ME&<ODO.OGI Pro(le* +e)ini!ion 6he simulation of the propaneFpropylene splitting unit /as carried out using ,ysys 5imulation tool and the result obtained from the simulation /as analyKed using 2initab 1& statistical soft/are6he propylene ^ propane unit in this case study /hich is conceptually illustrated in Aigure 1, is a part of a polypropylene plant /hich comprises propylene purification, polymeriKation, additiGe and e3trusion units- 6he plant /as designed to produce *#,$$$ metric tonnes of polypropylene resin per year (1digo, %$$*)- 6he purification area upgrades "* mole percent propylene from a fluid catalytic cracDing (A++) unit to a minimum of (& moles percent in the propylene F propane splitter6he propyleneF propane splitter is column of * m* and contains a total of 1#$ trays, a reboiler and an oGerhead condenser- 6he purified propylene recoGered at the top is condensed, part of /hich is returned as reflu3 and the other part fed to the propylene drying unit, /hile the propane is dra/n off at the reboiler6he sensitiGity analysis /as carried out to study the interactiGe effect of those process Gariables inGolGed in the design and operation of the propaneFpropylene splitter case study- 6he analysis proGides a tool that is useful in the optimiKation of the operating condition of an e3isting propaneFpropylene splitting unitAigure 1- 5chematic of ?ropyleneF ?ropane 5plitter Pro"ess #imulation <n this /orD, the number of theoretical stages reJuired for the separation, feed stages location, reflu3 ratio, column pressure and reboiler duty /ere eGaluated- <n the performance analysis it /as possible to GisualiKe the effect of t/o Gariables on a specific design condition using response surface plots- 6he efficient operating criteria considered /as mole fraction of propylene in the distillate, /hich should be a minimum of $-(&Aor the simulation, the initial operating data of the column consisted of ##-*% Dg

moleEhr of propylene, the reflu3 ratio of 1$-%, the distillate flo/ rate of %&'-() Dg moleEhr, column pressure of 1)-%* atm and feed temperature of #*$+6E#5.& 'ND DI#C5##ION 6he propyleneF propane splitter /as simulated to study the interactiGe effect of those process Gariables inGolGed in its design and operation- 6able 1 sho/s the initial operating conditions and the material and energy balances obtained from the simulation- 6he response surface methodology /as used to obtain the surface and contour plots from the simulated data to describe the interactiGe effect of the process Gariables on percentage propylene yield in the distillate- 6he column /as optimiKed using 2initab 1&, to obtain m (#7 propylene in the distillate from the (&7 minimum /hich /as the specified separation for the propaneFpropylene splitter in the case study plant6able 1- <nitial ?lant 1perating 0ata <tem Aeed ?roduct @ottom Material stream Capour Araction 1-$$ $-$$ $-$$ 6emperature 8+9 #*-$$ &1-"# #&-%& ?ressure 8bar9 1)-%* 1"-%% 1(-%# 2olar Alo/ 8DgmoleEh9 %($-"$ %&'-(' &*-"& 2ass Alo/ 8DgEh9 1%*&&-*" 1$&1(-)$ 1(%&-#" .iJuid Colume Alo/ 8m*Eh9 %*-)% %$-$* *-"( ,eat Alo/ 8DcalEh9 F%%")#'-(' F&*-)* F11#')'(-"" Component Mole !ra"tion ?ropylene $-)1 $-(&' $-$&* ?ropane $-1( $-$#& $-(#" Energy #tream Oc Or ,eat Alo/ 8DcalEh9 )&##&1$-$) "#*$1$%-"1 Effe"t of 6eflu? 6atio and Column Pressure 6he effect of reflu3 ratio and column pressure on the percentage composition of propylene in the distillate is presented in Aigure %- <t /as obserGed that at a column pressure of %% atm and reflu3 ratio of 1$, the percent of propylene obtained in this distillate /as in the range of (&-7 to (&-&7- >t a lo/er pressure of 1)atm using the

same reflu3 ratio of 1$, the percentage composition of propylene /as obserGed to increase to a higher range of (&-)7 and (#-%7- 6hus lo/ering the column pressure of
pressure reflu? 1" 1) 1( %$ %1 %% %* 11-% 11-$ 1$-) 1$-' 1$-& 1$-% 1$-$ (-)
,old Calues feed stage #$ 7 propylene (&-$ F (&-& (&-& F (&-) (&-) in distillate F (#-% P (#-% U (*-' (*-' F (&-$

Aigure %- +ontour ?lot of 7 ?ropylene in 0istillate Cs 4eflu3 4atio, ?ressure (atm)the splitter unit /ould faGor the purity of propylene in the distillate but /ould lead to an increased reboiler duty- 6hus it is adGisable that, selecting the column operating pressure must ensure that the de/point of the distillate is aboGe that /hich can easily be obtained /ith cooling /ater- <n general the contour plots in Aigures %, * and & indicate that increase in the reflu3 ratio increases the percentage propylene in the distillate /hile a decrease in pressure /ill faGor high yield of propylene- 6hus from the plots it /as found that for a yield of propylene aboGe (#-% 7 a column pressure of less than %$ atm and a reflu3 ratio of 1$-% /ere reJuiredEffe"t of !eed #tage .o"ation 6he interactiGe effects of feed /ith pressure and reflu3 ratio in Aigures * and & are Gery similar- <t /as obserGed that as the feed stage descends from stage %$ to stage '$ the
pressure feed stage 1" 1) 1( %$ %1 %% %* )$ "$ '$ #$ &$

*$ %$
,old Calues reflu3 1$-# 7 propylene (*-$ F (*-# (*-# F (&-$ (&-$ in distillate F (&-# (&-# F (#-$ (#-$ F (#-# P (#-# U (%-# (%-# F (*-$

Aigure *- +ontour ?lot of 7 ?ropylene in 0istillate Cs Aeed 5tage, ?ressure (atm)purity of propylene in the distillate increases- ,o/eGer, at a feed stage of "$ a gradual decline in composition of propylene is obserGed- 6he analysis further sho/s that, for optimum yield of propylene, the feed stage should be located bet/een stages #' and "#- ,o/eGer, the operator may choose not to obtain the optimum propylene yield of (#-#7 and aboGe since the pressure and reflu3 ratio may lead to high reboiler dutyreflu? feed stage (-) 1$-$ 1$-% 1$-& 1$-' 1$-) 11-$ 11-% )$ "$ '$ #$ &$ *$ %$
,old Calues pressure %$ 7 propylene (*-# F (&-$ (&-$ F (&-# (&-# in distillate F (#-$ (#-$ F (#-# P (#-# U (*-$ (*-$ F (*-#

Aigure & +ontour ?lot of 7 ?ropylene in 0istillate Cs Aeed 5tage, 4eflu3 4atio6eboiler Duty Consideration Dreboiler $eL,;"alKh% ' " %$ %% pressure 1' 1) ) ( 11-$ 1$-# reflu? 1$-$ Aigure #0 5urface ?lot of Oreboiler (e+'DcalEh) Cs 4eflu3 4atio, ?ressure (atm)

(,old Calueh Aeed 5tage #$) 6hus the effect of the pressure and reflu3 ratio on the reboiler duty (Oreboiler) on the one hand and of the pressure and feed stage on the reboiler duty on the other hand are sho/n in the surface plots in Aigures # and ' respectiGely>s it is eGident from Aigure #, high percent yield of propylene reJuires high reflu3 ratio and lo/er pressure /hich result in increased reboiler duty- > similar surface plot in Aigure ', sho/s that a high propylene percent in the distillate is promoted by a high feed stage and a reduction in column pressure /hich again increase the reboiler heat duty- <n this respect more utilities /ill be reJuired /hich /ill negatiGely affect the operating cost and profitability of the plant6he aim of any process plant is to maDe profit by minimising the cost of production- 6he cost of energy is a maLor factor to be considered especially in a deGeloping country liDe ;igeria /here energy is Gery e3pensiGe- 6he simulation and the analysis of the unit Aigure '- 5urface ?lot of Oreboiler (e+'DcalEh) Cs Aeed 5tage, ?ressure (atm)(,old Calueh 4eflu3 4atio 1$-#) should offer an aGenue for proper monitoring and optimiKation of the operation6esponse Optimi@ation Dreboiler$eL,;"alKh% "-$ "-# 1' 1) %$ %% pressure )-$ %$ "$ &# feed stage Aigure ", is the response optimiKation of the propaneFpropylene splitter unit carried out /ith 2initab 1& statistical soft/are to ma3imiKe propylene yield in the distillate and minimiKe the reboiler dutyHi 0.91341 Lo D Optimal Cur d = 0.83432 Minimum

Qreboile d = 1.0000 Maximum % propyl y = 7.0828 y = 95.0000 20.0 80.0 9.6591 11.3409 16.6364 23.3636 pressure reflux feed sta [20.1993] [10.0228] [51.9880] Aigure "- 4esponse 1ptimiKation for ?ropylene Yield 6he efficient operating criteria considered for the splitter unit /ere a minimum of $-(& mole fraction and a target of $-(# mole fraction of propylene in the distillate /hich represented the desirability limits for propylene ma3imiKation- 6he simulated propyleneFpropane plant in the case study produced ("&"-)DgEh of polymer grade propylene /ith a Juality of (&-"%7 propylene- 6he reboiler energy reJuirement for the column obtained in the simulation /as "-#31$' calEh and this /as considered as upper limit for reboiler heat duty /hich /as subLect to be minimised6he result of the optimiKation gaGe P(#7 propylene in the distillate and "-$)31$' D calEh heat flo/ in the reboiler /as achieGed at a column pressure of %$-1(( atm, reflu3 ratio 1$-$%* and at a feed stage of #% as the optimum condition of operation- 6he results haGe illustrated that despite an increase in the column pressure from 1) atm to %$-% atm, reduction in reflu3 ratio from 1$-% to 1$-$%, the reboiler heat duty reduced from "-#31$' to "-$)31$' NcalEhCONC.5#ION ?ropyleneF propane splitter in a petroleum refining case study has been simulated>nalysis of the data and optimiKation of the column haGe sho/n a reduction in reflu3 ratio from 1$-% to 1$-$%, an increase in the column pressure from 1)-%* atm to %$-%atm,

increased percent propylene in the distillate from (&-"7 to P(#7 and a saGing of about $-&31$' DcalEh in reboiler energy input- 6he results obtained haGe led to a better understanding of the process and haGe therefore proGided a guide to its optimum operation and control- 5imulation in this /orD /as carried out by using ,ysys and 2initab 1& 5oft/are /as used in analyKing the data6E!E6ENCE# +hen , and .in Y- (%$$1)- g +ase 5tudies on 1ptimum 4eflu3 4atio of 0istillation 6o/ers in ?etroleum 4efiningu- 6amDang Mournal of 5cience and :ngineering, Col&, ;o%, 1$#F11$0oughlas M- 2-(1()))- +onceptual 0esign of +hemical ?rocesses- 2c=ra/ ^ ,ill @ooD +ompany, ;e/ YorD,agger @- (%$$))- g<mproGing 4efinery 0istillation 1perationsu- ?6O O%, 1%(F 1*%,eiarittKF >drain 2 and IenKel 5- (%$$))- g>dGanced ?ropane 0ehydrogenation-u ?6O, )*F(1,ill 0- >nd Mustice A- +- (%$11)- gBnderstand 6hermodynamics to <mproGe ?rocess 5imulationsu- +hemical :ngineering ?rogress, %$F%#2artin =-0-, .atour ?- 4- and .ynn >- (1()1)- g+losed ^loop 1ptimisation of 0istillation :nergyu- +hemical :ngineering ?rogress, **F*"1digo @- 1- (%$$*)- g :Galuation of ?ropane ^ ?ropylene 5plitter in I4?+u- ;5: 6echnical 4eport?erry 4- ,-, =reen 0- I- and 2aloney M- 1- (%$$))- +hemical :nginersv ,anbooD)th :dition-5ection 1*F%)- 2c=ra/F ,ill @ooD +ompany, ;e/ YorD5innot 4- N-, +oulson M- 2- and 4ichardson M- A- (%$$))- +hemical :ngineering 0esign- Col', &th :dition, &(*F '*'- @utter/orthF ,einemam, 13fordP-16 SYNTHESIS OF FLEXIBLE POLYURETHANE FOAM USING CASTOR OIL/POLYOL AS A MONOMER 1Ogunfeyitimi, O. S., 2 Okewale, A.O., 3Igbokwe, P.K. 1. Vitafoam Nigeria Plc, Jos, Plateau State, Nigeria 2. Chemical Engineering Department, Landmark University, P.M.B.1001, Omu-Aran, Kwara State, Nigeria. 3. Chemical Engineering Department, Nnamdi Azikiwe University, P.M.B. 5025, Awka, Anambra State, Nigeria. ABSTRACT The importance of castor oil/polyol as a monomer has been explored in this work in order to evaluate its use in the synthesis of flexible polyurethane foam. The cost benefit analysis carried out on the various samples of flexible polyurethane foam produced shows a significant decrease of 9.5% in the cost of production when compared with foam produced

with 100% polyol. The study indicates that castor oil can be blended up to 25% with polyether polyol in the flexible polyurethane foam formulation. It is established that the products of this formulation can be used for all flexible foam applications while 30% blend of castor oil with polyether polyol shows wide variations in mechanical tests value from the recommended values of National standard. KEYWORDS: Polyurethane, Polyether polyol, Flexible Foam, Castor oil INTRODUCTION Improving the quality and cost effectiveness of polyurethane foam demands a constant search for new and renewable active monomer in the foam production. The use of a nonconventional chemical like castor oil as monomer in the production of polyurethane foam is being proposed. Foam manufacture is a combination of science and technology which is an integral part of everyday life. The commercial products known as polyurethane are complex polymeric materials usually formed by the reaction of liquid isocyanate component. Polyurethane chemistry is based on the reactions of isocyanates with active hydrogen containing compounds. Isocyanates are compounds having one or more of the highly reactive isocyanate group (-N= C= O). This group will readily react with hydrogen atoms that are attached to atoms more electronegative than carbon (Prashantha et al, 2001). The polyurethane polymer-forming reaction occurs between an isocyanate and an alcohol as follows: A urethane linkage is produced by reacting an isocyanate group, -N=C=O with a hydroxyl (alcohol) group, -OH. A poly-isocyanate is a molecule with two or more isocyanate functional groups, R-(N=C=O)n m2 and a polyol is a molecule with two or more hydroxyl functional groups, R'-(OH)n m2. The reaction product is a polymer containing the urethane linkage, -RNHCOO R'-. Polyurethane is produced by the poly addition reaction of a liquid poly-isocyanate with liquid blends of polyols in the presence of a catalyst and other additives (Kumar and Kaur, 2013). Flexible polyurethane can be broadly divided into two groups, namely viz; polyester and polyether foam. Two main classes of polyols are used in polyurethane manufacture, polyether polyols and polyester polyols. Polyether polyols provide unusually high hydrolytic stability and good low temperature flexibility. Their viscosity is relatively low. Polyester polyols provide superior mechanical properties, such as tensile strength, abrasion, and wear resistance, as well as solvent and oil resistance, to the polyurethanes in which they are used (Nexant, 2004). Polyurethanes result from the reaction of polyols with isocyanates. Polyurethanes are also used in coatings, adhesives, sealants, and elastomers (Nexant, 2004). Polyester foams are produced using polymeric polyol containing ester groups in the molecular chain or inside chains while polyether foams are produced using polymeric polyol containing ether linkages (carbon-oxygen-carbon links) in the main molecular chain or inside chains (Herrington, 1991). The more widely used polyether polyol have a relatively low molecular weight in the range of 500 to 3000 and are manufactured from propylene oxide and ethylene oxide (Hochte, 1952 in Herrington, 1991). The first foams were based primarily on the reaction of an aromatic isocyanate with a polyester polyol. However, these foams proved unable to withstand many in-use temperature and humidity conditions and often failed by crumbling away (Herrington, 1991). Better performance was obtained with foams based on

polyether polyols. Poly ether foam is more recently developed and is known to have many advantages over polyester foam which include; good elasticity, one shot production eliminating pre-mixing, less expensive in production and wider applications compared to polyester foam (Hamid, 2006). It is therefore imperative to find a suitable raw material (substitute) that can be used for the production of polyurethane foam in place of polyol or as interpenetrating polymer networks(IPNs) to cushion the high cost of importing polyol into the country which serves as the main raw materials in polyurethane foam production. The production of polymers from renewable sources such as vegetable oil-based materials is currently receiving attention because of the economic and environmental issues (Tsujimoto, 2004). Castor oil, a renewable material is known to have some properties in common with polyether polyol and this therefore necessitated this research in search for replacement or blending polyether polyol with locally sourced castor seed oil. In this work, production of flexible polyurethane foams using locally sourced castor oil in place of imported polyether polyol blend in different ratio, physico-mechanical and various mechanical tests analysis on the samples of flexible polyurethane foams produced were undertaken and compared with the polyurethane foam produced from 100% polyether polyol. The major constituent of castor oil, ricinoleic acid (12-hydroxy-cis-9-octadecenoic acid), is a hydroxyl containing acid (Baber, 2002). MATERIALS AND METHODS Castor seeds were obtained from Otukpo, Benue State, Nigeria. The oil was extracted through solvent extraction with n-hexane as the solvent at temperature of 60oC to 80oC in a soxhlet extractor using the method of (Ogunniyi et al, 1996). The castor oil was tested for colour, specific gravity, iodine value, acid value, Saponification value, and solubility in ethanol using the test methods of (Weiss, 1983; AOAC, 1980). Toluene diisocyante polyol, polyol, stannous octoate, dimethyl ethyl amine, DMEA, silicone oil and methylene chloride were obtained from Vitafoam Nigeria Plc, Jos and Chellarams Chemicals Plc, Lagos, Nigeria. Physico-mechanical characterization carried out on the polyurethane foam produced include; density, compression test, tensile strength and elongation at break, heat elongation at break, aging tensile strength, and hardness test (IFD), sag factor test, and porosity using the standard test method (ASTM D 3574). EXPERIMENTAL PROCEDURE Twenty-one kg/m3 density was chosen for the polyurethane foam produced based on market survey. Castor oil at 21oC, polyol (21oC) and TDI were weighed using weighing balance in separate containers. Water, amine, and silicone oil were also weighed separately using a weighing balance. This was poured into the castor oil/polyol container and it was stirred well with an electric stirrer. Afterwards, stannous octoate was then added and stirred for 10seconds after which TDI was added and mixed rapidly for 6 8 seconds. This mixture was then poured gently into the prepared mould. The cream and rise time were recorded using a stop watch. The foam was removed from the mould for visual and touch inspections. The foam samples were aerated for 18hours before the various mechanical tests were carried out so as to ensure complete curing. Stirrers and containers were cleaned using methylene chloride solvent. A TDI index of 107 was used to calculate the amount of TDI needed in part per weight of polyol/castor oil based on the calculation from the formulation.

Cost of Foam Calculation In foam calculations, it is assumed that all of the water totally reacts to yield carbon dioxide gas (Ogunniyi et al, 1998). The calculation of weight loss due to water is: Gas loss = wt. of water x Molecular Weight of CO2 = wt. of water x 44 Molecular Weight water 18 = 0.018 *2.44 = 0.04392kg Dry weight of foam = Wet weight of foam Gas loss Therefore, cost of foam = Total cost of raw materials Dry weight of foam RESULTS AND DISCUSSION The properties values of the castor oil used were presented in table 1.0. Comparison of these values with the literature shows little or no variation with the literature values cited. However, the mechanical properties of the various samples of polyurethane foam produced are shown in table 2.0. So formulation (0% castor oil) was taken as a control formulation for the polyurethane foam produced. Formulation S1, S2, S3, S4, S5, and S6 contains 5%, 10%, 15%, 20%, 25%, and 30% castor oil respectively. The foam produced is yellow in colour. This can be attributed to the colour of castor oil which is naturally yellow. Effect of Process Parameters on Polyurethane Foam Produced from Castor oil/Polyol Table 3.0 results indicate that the tensile strength of the foam produced increase with increasing amount of castor oil used in the formulation. The compression set increase as the quantity of castor oil increase for all the samples except that of S3. This could be probably due to the cleavage of rigid cross - links formed between castor oil and toluene diisocyanate which prevented substantial elastic recovery (Ogunniyi et al, 1998). It was revealed from table 3.0 that all the foam samples produced with the blended castor oil compared favourably with the set standard of K10% (NIS 295:1993) for compression tests of polyurethane foams except that of sample 6 which differs. The tensile strength values for all the various foam samples produced compare favourably with the So tensile strength values except that of sample S6. Elongation at break values decrease with increase in castor oil quantity except that of S1 which was greater than that of So sample. Foam sample produced with 25% castor oil blended with polyol showed a good result when compared with foam produced with 100% polyether polyol except sample 6 where high tensile force is required to stretch the polyurethane foam to breaking point. This indicates that foam produced with high load of castor oil will exhibit very poor tear strength which can be attributed to the two functional groups (double bond and the hydroxyl group) present in castor oil which played a mojor role in the synthesis of the polyurethane foam as the proportions of it is increased in the formulation (Petrovic, 2000). Also, the density of foam samples produced increase with increase in castor oil but the densities of S1, S3, and S4 compared favourably with the chosen density of polyurethane foam chosen based on the market survey. This implied that higher load bearing capacity can be achieved with increased castor oil ratio in foam formulation. The properties of S6 indicate hardness and rigidity of the foam sample this could be explain by the interpenetrating polymer network of the castor oil which suggests the foam to be semi-rigid. The flammability nature of all the foams samples were tested as the sample continues to burn when exposed to

naked fire. It can be seen in Table 3.0 that the support factor for all the foam samples of the polyurethane foams produced with the castor oil blend of polyether polyol fell within the set standard range of (2.4 3.0) (ASTM D 33574). This revealed that the polyurethane foam produced from the blend of polyether polyol and castor oil has the ability to provide support. It is to be noted that the porosity of the foam samples decrease with increase in castor oil but the porosity value of S6 is too low compare to the So. All the flexible polyurethane foam samples produced has their porosity values lie between the Standard Organization of Nigeria set porosity standard limit of 45%KPorosityK80% for all polyurethane foam except sample 6. This shows that all the foam samples produced has open cells except that off S6. The indentation force deflection also confirms that the S1 to S5 blend of castor oil with polyol could yield good flexible polyurethane foam. Table 4.0 shows the summarized price of each samples of polyurethane foam produced per kilogram of foam samples. It is evident from the table that the price decreased as the proportions of castor oil/polyether polyol in the polyurethane foam is increased. It showed a 9.5% decreased in cost compared to 100% polyol flexible polyurethane foam. Table 1.0 Properties of Castor Oil Property Solvent extraction from Literature (Kirk-Othmer,1964) Solvent Extraction (Ogunniyi et al, 1998 Values of Castor Oil used for Experimentation Specific gravity at 25oC 0.961 0.963 0.859 0.960 Appearance Clear Clear Clear Refractive Index at 25oC 1.4764 1.475 Colour Yellow Yellow Yellow Acid Value 3 3 2 Hydroxyl Value 164 166 Iodine Value 82 88 85.65 83 Saponification Value 179 185 180 181 Solubility in Alcohol Complete Complete Complete Water content% 0.3 Source: Kirk-Othomer, 1964 and Ogunniyi et al, 1998. Table 2.0 Formulation of Polyurethane Foam Produced Materials S0 (g) S1(g) S2(g) S3(g) S4(g) S5(g) S6(g) 0% castor oil 5%

castor oil 10% castor oil 15% castor oil 20% castor oil 25% castor oil 30% castor oil Polyol 400 380 360 340 320 300 280 Castor oil 0 20 40 60 80 100 120 OH value 42 48.1 54.2 60.3 66.4 72.5 78.6 TDI (index= 107) 212.3 216.1 219.8 223.6 227.4 231.2 235.0 Silicone 3.6 3.6 3.6 3.6 3.6 3.6 3.6 Amine 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Tin catalyst 0.6 0.6 0.6 0.6 0.6 0.6 0.6 water 18 18 18 18 18 18 18 Table 3.0 Physico-mechanical Properties of Polyurethane Foam Produced Test methods S0 S1 S2 S3 S4 S5 S6 Density(kg/m3) ASTMD 3574, NIS 295: 1993 21.06 21.07 21.10 21.08 21.07 21.12 22.21 Compression set (%) 10% max ASTMD 3574 7.14 7.22 8.13 7.89 8.22 8.76 14.65 Elongation at break (%)
ASTM D 3574

NIS 295: 1993 (120% Min) 134.98 135.42 129.56 125.78 126.67 125.38 110.43

Heat elongation at break (%)

NIS 295: 1993 (130% Min) ASTM D 3574 137.34 137.66 133.56 131.36 132.56 130.45 112.34

Tensile strength (KN/m2)

ASTM D3574 (98 Min) 104.17 105.55 105.87 106.25 106.06 105.98 122.6

Porosity
ASTM D3574 (40min and 80 max)

70 67 65 62 60 57 37 Ageing Tensile strength(KN/m2)

ASTM D3574

105.34 107.23 107.23 107.43 107.39 107.44 132.33

Indentatio n force deflection (IFD)(N) 75/25

ASTM D 3574

113.00 113.00 111.00 113.00 114.00 114.00 133.00

60/40
ASTM D3574, NIS 295:1993

128.00 129.00 133.00 143.00 147.00 146.00 154.00

35/65 ASTM D 3574

291.00 294.00 263.00 273.00 302.00 302.00 372.00

Support factor (65/25) ASTMD3574 2.58 2.60 2.39 2.42 2.65 2.65 2.80 Rise time (secs) NIS 295:1993 88 93 98 101 106 110 132 Cream Time (secs) NIS 295:1993 13 14 17 19 20 23 29 Table 4.0 Summary Cost of Various Samples of Polyurethane foam Produced Sample (So) Raw materials Cost/kg (M) Amount (M) Polyol 379 151.6 Castor oil 120 0

TDI 608 128.896 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Nil Total 285.9624 Gas loss (0.04392) Cost/kg of wet foam

w450.3345
Cost/kg of dry foam w483.80 Sample (S1) Raw materials Cost/kg (M) Amount (M) Polyol 379 144.02 Castor oil 120 2.4 TDI 608 131.328 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Nil Total 283.2144 Gas loss (0.04392) Cost/kg of wet foam

w443.215
Cost/kg of dry foam w475.93 Sample (S2) Raw materials Cost/kg (M) Amount (M) Polyol 379 136.44 Castor oil 120 4.8 TDI 608 133.76 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Nil Total 280.4664 Gas loss (0.04392) Cost/kg of wet foam

w436.1841
Cost/kg of dry foam w468.16 Sample (S3)

Raw materials Cost/kg (M) Amount (M) Polyol 379 128.86 Castor oil 120 7.2 TDI 608 136.192 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Nil Total 277.7184 Gas loss (0.04392) Cost/kg of wet foam

w429.2402
Cost/kg of dry foam w460.50 Sample (S4) Raw materials Cost/kg (M ) Amount (M) Polyol 379 121.28 Castor oil 120 9.6 TDI 608 138.016 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Nil Total 274.3624 Gas loss (0.04392) Cost/kg of wet foam

w422.096
Cost/kg of dry foam w452.68 Sample (S5) Raw materials Cost/kg (M) Amount (M) Polyol 379 113.7 Castor oil 120 12 TDI 608 140.448 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Total 271.6144

Gas loss (0.04392) Cost/kg of wet foam

w415.312
Cost/kg of dry foam w445.21 Sample (S6) Raw materials Cost/kg (M) Amount (M) Polyol 379 106.12 Castor oil 120 14.4 TDI 608 142.88 Silicone 1100 3.96 Stannous Octoate 1920 1.152 Amine 443 0.3544 Water Total 268.8664 Gas loss (0.04392) Cost/kg of wet foam

w408.61
Cost/kg of dry foam w437.84 ACKNOWLEDGEMENT The Vita foam Nigeria Plc., Jos is acknowledged for the use of their laboratory and supply of some materials that was used in this work. CONCLUSION The use of castor oil as a reactive monomer in the synthesis of polyurethane foams has been investigated and the synthesis potential confirmed. The study indicates that castor oil can be blended up to 25% with polyether polyol in the flexible polyurethane foam synthesis. It is established that the products of this formulation can be used for all flexible foam applications while 30% blend of castor oil shows a wide variations from the National standard values with respect to density, porosity, and compression and elongation tests. The cost analysis shows that the use of castor oil - polyether polyol in polyurethane foam production is cost effective commercially. REFERENCES 1. AOAC, (1980), Official Methods of Analysis, Association of Official Analytical Chemists, 12th ed., Washington D. C., U.S.A. 2. Baber, T. M., Vu, D. T., and Lira, C. T., (2002), LiquidLiquid Equilibrium of the Castor Oil + Soybean Oil + Hexane Ternary System, Journal of Chemical and Engineering Data, 47, PP. 1502-1505. 3. Billmeyer, F. W., 1984, Textbook of Polymer Science, Wiley Interscience Publishers, New York, 3rd ed., PP. 446-448. 4. Hamid, Y., Hojati-Talemi, P., (2006), Preparation and properties of novel biodegradable polyurethane networks based on castor oil and Poly (ethylene glycol), Polymer Degradation and Stability, Vol. 92, PP. 480-489.

Herrington, B. S., (1981), Water blown Urethane Foam, Journal of Cellular Plastics, 17, PP. 333. 5. Herrington, B.S., Nafziger, L., Hock, K., Moore, R., Casati, F., Lidy, W., (1991), Flexible polyurethane foam Dow Chemical Company., Midland, MI, USA. 6. Kirk-Othmer, (1964), Encyclopedia of Chemical Technology, 2nd ed., Vol. 4, John Wiley and Sons, New York, PP.524. 7. Kumar M. and Kaur R., (2013), Effect of Different Formulations of MDI on Rigid Polyurethane Foams based on Castor Oil, International Journal of Scientific Research and Reviews, 2(1) Suppl., PP. 29- 42. 8. Nexant, (2004), Process Evaluation/Research Planning Programme New Report Alert, Nexant Chemical Systems, New York, U.S.A., PP. 1 6. 9. Ogunniyi, D.S., Fakayejo, W.R.O, and Ola, A., (1998), Industrial Utilization of Castor oil 1: Polyurethane Foam Synthesis and Properties, Journal of the nigeria Society of Chemical Engineers, 17, PP. 40 43. 10. Ogunniyi, D.S., W.R.O. Fakayejo and A. Ola, (1996), Preparation and properties of polyurethanes from toluene diisoyanate and mixtures of castor oil and polyol, Iranian Polymer Journal, 5, PP. 5659. 11. Petrovic, Z.S., Guo, A., Javni, I., and Zhang, W., (2000) , Effect of structure on Properties of Soy-cased polyols and Polyurethanes, Polyurethanes Conference, Boston, U.S.A., PP. 323. 12. Prashantha, K., Sherigara, B.S., Pai, K., Vasanth, K., and Prasannakumar, S., (2001), Interpenetrating polymer network based on polyol modified castor oil polyurethane and poly (2-hydroxyethylmethacrylate): Synthesis, chemical, mechanical and thermal properties. Bulletin of Material Science, 24, 5, PP. 535-538. 13. Tsujimoto, T.; Uyama, H., and Kobayashi, S., (2004), Macromolecules of Polyol Polyurethanes foam, Journal of Polymer Science, 37, PP. 1777. 14. Weiss, E. A., (1983), Oilseeds Groups, Tropical Agriculture Series, Longman Scientific and Technical.

P-17 THE ROLE OF CATALYSIS IN THE DEVELOPMENT OF THE PETROCHEMICAL INDUSTRY IN NIGERIA
Abdulazeez R. Isa*, Sharafadeen Gbadamosi, Opeoluwa O. Fasanya, Abubakar I. Yusuf, Aishat Osigbesan, Olabode H. Olabimtan, Hayatudeen Aminu, , Abdulazeez Y. Atta. National Research Institute for Chemical Technology, Zaria. * rbed.abdul@gmail.com Abstract The Nigerian Industrial Revolution Plan (NIRP) inaugurated by the Federal Government in May 2012 is meant to serve as a means of increasing the GDP of the country via industrialization of some of Nigerias key strengths. Some areas of focus include agriculture, textiles, solid minerals and petrochemicals industry. The petrochemical industry is one of the priority subsectors that will receive rapid ramp-up. Revitalizing this sector will encourage high value-added downstream investments, and build institutional strengths to attract chemical-related clusters and advanced skills. A core field that is required for petrochemical production is catalysis. Petrochemical industries rely on catalysts to produce chemicals that

are essential to the modern prosperous life. These catalysts are the key enablers in 90% of chemical manufacturing processes. That means catalytic science and technology is at the core of any nations economic and energy security future. It is an underpinning science for many present and future technology needs. Nigeria needs the knowledge that catalysis research can provide as it marches towards industrialization. Introduction Crude oil and natural gas are presently the main foreign exchange earners for Nigeria. These resources are predominantly exported without value addition. There is need to transform the non renewable resources into valuable petrochemicals which will result into creation of much needed jobs, increase the foreign receipt by exporting the petrochemicals and enhance technological development of the country. Nigerias petrochemical industry has been largely unexploited and thus local research and technological developments remains little. Numerous opportunities for research and development exist in the Nigerian petrochemical industry and one important field of knowledge that is necessary for petrochemicals development is catalysis. Catalysts are valuable materials in the chemical process industry and are used for the production of transportation fuels, the production of bulk and fine chemicals and the prevention of pollution by avoiding formation of unwanted products especially in automobiles; to name a few applications. Catalysts have been used to improve process economics for over two hundred and fifty years since their first industrial use in 1746 by J. Roebuck for the manufacture of lead chamber sulfuric acid. Presently due to environmental issues, catalysis appears even more important than it ever did in developed societies (Fechete, et al., 2012). It is generally agreed that science and technology drive the development of any nation. A look at countries such as china and the USA will show the positive impact of investments and policies by their various governments and private institutions in science and technology. Strong government support and policy direction in Europe and the US led to development of large petrochemical clusters which cater for most of their local needs. Production of Catalysts and the development of the science of catalysis are definitely significant to the progressive development of any economy, especially that of a country heavily reliant on its oil and gas industries. Most of the processes in petroleum refining and petrochemicals are catalytic in nature. The basic refining operations are atmospheric and vacuum distillation units, naphtha hydrotreating, distillate hydrotreating, FCC, FCC hydrotreating, hydrocracking and naptha isomerization units (Figure 1). Apart from atmospheric and vacuum distillation units, all others units are catalysts dependent as shown in Figure 1. A survey in the united states of America between 1998 and 2002, put the world market for catalysts at about 9 billion US dollars (Centi, et al., 2002), (Armor, 2011) with the demand forecasted by the Freedonia group to grow to about 16.3 billion US dollars as of 2012 (Armor, 2011). Refining and petrochemical catalysts as of 2007 constituted approximately 35% of a $14.5 billion dollar global catalyst market (Degnan Jr, 2007).
Crude Distillation Unit D e sa lte d C ru d e O il L ig h t Stra ig h t R u n N a p h th a Ke ro se n e Mid d le D is tilla te A tm o sp h e ric G a s O il Vacuum Distillation Unit Gas C o n ce n tra tio n G a s o lin e Ke ro se n e

Je t F u e l D ie se l L u b e O ils A sp h a lt F u e l O il S olid F u el L eg en d C a ta ly tic U nit N o n C a ta ly tic B la c k O il U n it

H yd ro c ra c k in g H yd ro tre a tin g FC C H yd rotre a tin g

C y c le O ils
C4 Isome r is a tio n A lk y la tio n C a ta ly tic C o n d en s a tio n H yd ro tre a ting R e fo rm in g L ig h t N ap hth a Hy dro tre a tin g Isome r is a tio n Hy dro tre a tin g

Figure 1 Catalyzed and Uncatalyzed Petroleum Refinery Operations Improved catalytic processes lower energy requirements, make better use of natural resources, reduce the amount of by-products formed and eliminate contaminant effluents. Petrochemical Catalysis In the petrochemical industry catalysts are required for the synthesis of intermediate chemicals and polymers. Basic petrochemicals include light olefins (e.g. ethylene and propylene) and aromatics, which are raw materials for making plastics, rubber and fiber. Petrochemical processes are mainly concerned with hydrogenation and transformation of olefins as well as the interconversion of alkylaromatics. Selective hydrogenation of petroleum fractions was first achieved in the 60s with the use of either active metals for sulfur free fractions or metal sulfide when the fractions have sulfur impurities. Pd catalysts are extensively used for selective hydrogenation of diolefins and light alkynes in the C2-C5 range and hydrogenation of sulphur free aromatics. Ni-Mo sulfide and passivated Ni are employed for hydrogenating olefins and aromatic steamed cracked gasoline containing sulfur traces respectively. In the 80s, it was reported that addition of Au to Pd improved significantly the selectivity of the catalyst. Total aromatic hydrogenation could be achieved using Ni catalysts for sulfur free feedstocks while, Pt is substituted for Ni if the feedstocks contains sulfur impurities (Marcilly, 2003). Polymerization of Olefins could be achieved over either Ziegler-Natta catalysts (mixture of solid and liquid compounds containing a transition metal such as Ti or V) or Phillips catalysts (hexavalent surface chromate on high surface area silicate support). However, these catalysts are now being replaced by single- site metallocene and postmetallocene catalysts. These new generation catalysts are employed for the manufacture of polymers with tailored structures. Addition of methyl aluminoxane to metallocenes is believed to enhance the activity of the catalysts (Deutschmann, et al., 2009). Alkylaromatics are interconverted via Isomerization, alkylation, transalkylation and disproportionation reactions. Industrial production to maximize p-xylene through isomerization process has been carried out in the 60s. Significant improvement was made in the 70s with the introduction of a more active mordernite and then in the 80s with the use of ZSM-5 catalyst by Mobil workers (Marcilly, 2003). Alkylation of aromatics is applied on a large scale in the chemical industries. Many industrial alkylation processes are still carried out with catalysts having drawbacks. These catalysts are strong mineral acids or Lewis acids often called Friedel-Crafts catalysts (HF, H2SO4, AlCl3) which are highly toxic and corrosive, but they have been recently substituted by zeolites owing to the latters environmental friendliness (Perego & Ingallina, 2002). Transalkylation and disproportionation are the main

processes for transforming aromatics, especially to dialkylbenzenes. As alkylation process, transalkylation and disproportionation processes are both acid catalysed. In the past, liquid Friedel-Crafts and HF-BF3 catalysts were employed. Subsequently, the metal oxide catalysts, like Co-MoO3 on aluminosilicate/alumina and noble metal or rare earth metals on alumina were developed and used. Nowadays, zeolite catalysts, like zeolite Y, mordernite, ZSM-5 and other large pore zeolites, are largely used. Transalkylation processes are mostly carried out with large pore zeolites which can also be used for toluene disproportionation. However, the latter is mostly catalysed by medium pore size zeolites such as ZSM-5 (Tsai, et al., 1999). Nigerian Petrochemical Industry Nigeria as one of the leading member of the OPEC countries has a petrochemical sector which has been evolving over the last twenty years. There are three major petrochemical industries of note in Nigeria, two of which are run by the Federal Government and the third, Indorama Eleme Petrochemical Ltd was privatized in 2006. The three petrochemical industries in Warri, Kaduna and Eleme were designed to get their feedstock from Warri, Kaduna and Port Harcourt refinery respectively. Table 1: Major Petrochemical Industries in Nigeria Name Location Products Capacity Technology Year of Commission Kaduna Refining and Petrochemical Company (KRPC) Ltd Kaduna Linear Alkyl Benzene 30,000 MTA UOP 1988 Benzene 15,000 MTA Heavy alkylate 2920 MTA Deparafinated kerosene 30,000 MTA Warri Refining and Petrochemical Company (WRPC) Ltd Warri Carbon Black 18,000 MTA

1988 Polyproylene 35,000 MTA Indorama Eleme Petrochemical Company Ltd Eleme Olefins 440 KTA M.W Kellog(USA) 1995 Polyethylene 360 KTA Nova Chemicals (Canada) Polypropylene 120 KTA Basell (Italy) Butene 1 22 KTA The petrochemical section of KRPC has been shut down since 1989 and that of WRPC last functioned in 1998 though that of WRPC was scheduled to resume operation in the third quarter of 2013. This lack of operation is due to poor governmental policies, repeated breakdown of various unit of the Warri and Kaduna refinery, and the vandalization of pipelines at the Niger Delta region of the country. The shortage of raw materials has resulted in some of the plants resorting to the recycling of scraps, and this has led to a progressive degradation in the quality of products. The Eleme Petrochemical Company (EPCL), which was built adjacent to the Port Harcourt refinery in 1995, was to get its raw materials directly from the refinery. However it was also operating at about 40% of its designed capacity due to various technical problems at that time. In August 2006, under the Privatization Program, the Indorama Group emerged as the core investor of EPCL and since then, become the Indorama Eleme Petrochemical Ltd (IEPL). Over the years, IEPL has recorded achievements of smooth and stable operations, enhanced production capacities, winning of several global awards and certificates, and has become a successful model of the Nigerias Privatization Program. President Olusegun Obasanjo, during his first tenure as a civilian president, commenced the deregulation of the petroleum and petrochemical sector. Part of his agenda was to turn Nigeria into a centre for production and export of petrochemicals in West Africa. Singapore based company; EUROCHEM Technologies got approval from the Nigerian government for the construction of a methanol to olefins plant; high-density polyethylene (HDPE) and polypropylene (PP) units in Lekki Export Processing Zone in the Ibeju Lekki area of Lagos. The complex is to be based around a 2.5 million tonnes/year single line methanol plant. When this facility is completed it is expected to be the world's largest singletrain methanol plant. The MTO unit is expected to be the first global facility to commercialize UOP/Norsk Hydro technology according to EUROCHEMs official website. Ethylene and propylene produced from the unit will feed a 400,000 tonne/year HDPE plant and a 400,000 tonne/year PP unit. EUROCHEM set up two subsidiaries, Viva Methanol and Axinova Polyolefins, which will operate the methanol plant and the MTO polyolefin production plants respectively. In October 2002, the Nigerian president laid the foundation stone for the complex. The products are meant be sold on the domestic market as well as in

sub-Saharan Africa and Western Europe. However, the propect is yet to be actualized. As of 2011, Nigeria had olefins production capacities of 300,000 tonnes per annum ethylene and 125,000 tonnes per annum propylene with thermoplastic resins capacities of 240,000 tonnes per annum linear low-density polyethylene (LLDPE) and 95,000 tonnes per annum polypropylene (PP). The main risks to growth in the market are unrest in the Niger Delta, which has reduced petrochemicals output, and the poor business environment climate. Petrochemical Catalysis research in Nigeria Petrochemical catalysis research and development should be directed at serving the needs of the country and also meeting global requirements. Raw materials for production of various catalysts are readily available in Nigeria. Kaolin is one of such materials which can be used for the synthesis of zeolite which have played a major role in petrochemistry in the twentieth century (Fechete, et al., 2012). Advances in the application of zeolitic materials as petrochemical and refining catalysts are continuously taking place. Among major refining and chemical processes, principal focus has been on expanding the compositional range and improving the quality and cost of the mainstay zeolites. The discovery, development and commercialization of new materials to suit specific selectivity, longevity or activity opportunities are also areas where focus has been concentrated on (Degnan Jr, 2007). This has led to exploration of local raw materials for zeolite production. Over 40 Kaolin deposits and occurrences have been recorded in Nigeria (Ekosse, 2010). Countries such as Botswana who also have huge Kaolin deposits have identified it as a possible future economic gateway (Ekosse, 1998). The use of Kankara kaolin clay as catalyst feedstock for the production of zeolite has been investigated by various researchers. Atta et al (2012) reported the synthesis of analcime zeolite from Kankara clay while the work of Amber et al (2012) focused on the synthesized Zeolite A also from Kankara clay gotten from Katsina State in Northern Nigeria. Zeolite X (Faujasite) has been successfully synthesized from Kankara kaolin clay (Atta, et al., 2007). Faujasite class of zeolites has a broad field of application as a component of cracking catalyst and also as hydrotreating catalyst modifier. They also went on to synthesize ZSM5 from Faujasite while Kovo (2011) worked extensively on the production of zeolites A,Y and ZSM-5 and zeolites membranes from Ahoko kaolin going on to develop a novel technique for metakaolinization. Conclusion Petrochemical industry is vital in modern economy because it provides the route in processing crude oil and natural gas which results in basic intermediate products and much needed societal needs. Catalysis is important in the processing of crude oil and natural gas. Catalysis research in Nigeria, especially for the petrochemical industry has been difficult due to various problems peculiar to development of education, science and technology in Nigeria. Lack of infrastructure and modern analytical equipment are major contributors to the dearth of catalysis research. For meaningful catalysis research, equipment for characterization such as XRD, XRF, TEM, SEM, AAS, BET and also microactivity reactors (fixed bed and fluidized bed) for catalyst testing have to be made available to researchers in universities and research institutes. Establishment and funding of catalysis centres of excellence by the government will go a long way in igniting concerted research efforts in petrochemical catalysis. In addition, major oil and gas companies operating in Nigeria should be made to

fund such research and development activities. References Amber, I., Folayan, C., Suleiman, R. & A.Y, A., 2012. Design, construction and testing of a solar adsorption refridgerator using synthesized Zeolite A and water as adsorbent/Adsorbate pair. Advanced Materials Research, Volume 367, pp. 495-500. Armor, J. N., 2011. A history of industrial catalysis. Catalysis Today, Volume 163, pp. 39.Atta, A.Y., Jibril, B.Y., Aderemi, B.O. & Adefila, S.S., 2012. Preparation of Analcime from Local Kaolin and Rice Husk Ash, Applied Clay Science, 61, pp. 8-13. Atta, A., Ajayi, A. & Adefila, S., 2007. Synthesis of Faujasite Zeolites from Kankarra Kaolin Clay. Journal of Applied Sciences Research, 3(10), pp. 1017-1021. Centi, G., Ciambelli, P., Perathoner, S. & Russo, P., 2002. Environmental catalysis: trends and outlook. Catalysis Today, Volume 75, pp. 3-15. Degnan Jr, T. F., 2007. Recent progress in the development of zeolitic catalysts for the petroleum refining and petrochemical manufacturing industries. s.l., Elsevier. Deutschmann, O., Knozinger, H., Kochloefl, K. & Turek, T., 2009. Heterogeneous catalysis and Solid Catalysts. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA. Ekosse, G., 1998. The Kaolin Industry in Africa: genesis, industrial applications, investment prospects and future economic trends.. Industrial Minerals, Issue 77, p. 372. Ekosse, G.-I., 2010. Kaolin deposits and occurences in Africa: Geology, minerology and utilization. Applied Clay Science, Issue 50, pp. 212-236. Fechete, I., Wang, Y. & Vedrine, J. C., 2012. The past, present and future of heterogeneous catalysis. Catalysis Today, Issue 189, pp. 2-27. Fechete, I., Wang, Y. & Verdine, J. C., 2012. The Past, Present and Future of heterogeneous catalysts. Catalysis Today, Issue 189, pp. 2-27. Kovo, A. S., 2011. Development of zeolites from zeolite membranes from Ahoko Nigerian Kaolin. s.l.:PhD Thesis submitted to The University of Manchester. Marcilly, C., 2003. Present status and future trends in catalysis for refining and petrochemicals. Journal of catalysis, Volume 216, pp. 47-62. Martinez, C. & Corma, A., 2011. Inorganic molecular sieves: Preparation, modification and industrial application. Coordination chemistry reviews, Issue 255, pp. 1558-1580. Perego, C. & Ingallina, P., 2002. Recent advances in the industrial alkylation of aromatics:new catalysts and new processes. Catalysis Today, 1-2(73), pp. 3-22. Tsai, T., Liu, S. & Wang, I., 1999. Disporportionation and transalkylation of alkylbenzenes over zeolite catalysts. Applied Catalysis A: General, Issue 181, pp. 355-398.

P-18 Functionalization of Zeolite A Synthesised from Nigerian Ahoko Kaolin for Adsorption Study of Methylene Blue
Alaya Sherifat and A.S. Kovo Department of Chemical Engineering, Federal University of Technology, Minna kovo@futminna.edu.ng, kovoabdulsalami@yahoo.com, 08094059107 Abstract The synthesis, characterization and functionalization of zeolite A for adsorption studies of Methylene blue (MB) were studied. The zeolite A was synthesised from Ahoko kaolin and functionalized using Hexamethyltetraamine (HMTA). This was confirmed by Fourier

Transform Infrared spectroscopy (FT-IR) analysis. The effects of initial concentration, adsorbent dosage, pH and temperature with contact time were studied in a batch system for both unfunctionalized zeolite A(UFZA) and functionalized zeolite A(FZA) under the following conditions; initial concentration of 100mg/L, temperature of 303K, and pH 7. The adsorption rate increased with increase pH, temperature, initial concentration but decreased with adsorbent dosage for both unfunctionalized and functionalized zeolite A. Langmuir, Freundlich and Timkin isotherm were investigated, Langmuir isotherm was found to be most suitable. Also, the pseudo- first order and pseudo- second order kinetic equations were evaluated and the adsorption of MB unto UFZA & FZA were found to conform to pseudosecond order kinetics. These results show that zeolite A synthesised from kaolin can be utilized for the removal of dyes such as MB from waste water. 1.0 Introduction Dyes are important substances which find applications in many chemical industries such as dying, plastics, leathers, paper and pulp (Nigam P, 2000). There are over 100,000 commercially available dyes with over 7x 105 ton of dye stuff produced annually (Nigam P, 2000). Dyes are classified as acidic, basic, direct, disperse, reactive, sulphur and vat. These different dye stuffs appear in effluent of some industrial wastewater (Ghoreishi, 2003) as shown by studies and are very difficult to remove, due to their recalcitrant organic molecules, resistant to aerobic digestion and their stability to light ( Fu, 2001). Thus, posing great danger to the ecosystem because it is highly visible, even in small amount and this influences the water environment considerably. Also, their ability to reflect sunlight has drastic effect on the growth of bacteria and biological activities (Fu, 2001). Hence, there is need for extensive research to find the effective and efficient alternative for the removal of dyes. The technologies used in removal of dyes is divided into three categories; biological, chemical and physical (Robinson, 2001). The physical (adsorption) has been recognized as a potential technology for dye removal because it is economical, effective and has simple design. However, the nature of adsorbate and its substituents greatly affects the adsorption process. Likewise, the properties of adsorbent such as porosity structure, chemical structure and concentration of surface functional groups, play important role in the adsorption capacity and the removal mechanism of the adsorbate (=upta, %$$#). Activated carbon has been the most popular adsorbent and has been used with great success. This is due to its high adsorption capacity, high surface area, micro porous structure and high degree of surface reactivity. But, its application is limited due to high cost and minimal decomposition, which may cause more environmental problems (Robinson, 2002). This has led to studying the feasibility of using inexpensive alternative materials by many investigators and these include clay (Bingol, 2010), sepiolite (Bingol, 2010), egg shell (Arami 2008), zeolite (Turan, 2005), wheat and rice (Aydin, 2008) among others. However, zeolite A has rarely been reported. More so, adsorption of dyes unto fuctionalized zeolite A has not been investigated. In this study, zeolite A was synthesised from AH kaolin, characterized and functionalized with HMTA for adsorption studies of MB in terms of the effect of initial concentration, adsorbent dosage, pH and temperature. 2.1 Materials and methods The raw kaolin used in this work was collected from Ahoko, Kogi state of Nigeria. 100g of

Ahoko kaolin collected was crushed using mortar and pestle, sieved using 250__ and thoroughly washed with distilled water. It was allowed to settle freely and the supernatant was collected. The supernatant was allowed to settle for 24hrs and the settled clay was obtained by decantation. The clay obtained was then dried overnight using GENLAB oven at 100oC. The surfactant HMTA used for functionalization of synthesised zeolite A and the MB used for adsorption studies were made by BDH Chemical Ltd, England. MB has a molecular weight of 319.852g/mol, molecular formula of C16H18N3SCl and the structural formula is Figure 1. Structure of methylene blue dye 2.2 Synthesis of zeolite A: The refined kaolin was metakaolinized at a temperature of 600oC for 1hr; it was then allowed to cool in air overnight. The aluminosilicate gel used for the synthesis of zeolite A was prepared from reaction mixture with molar composition 3.75Na2O:Al2O3:2.5SiO2:243.7H2O. 0.832 g of sodium hydroxide was measured and dissolved in 12 g of deionised water and stirred briefly for 5 min. 0.693 g of the metakaolin was then added to the mixture to obtain the synthesis mixture. The aluminosilicate gel was subsequently aged with continuous stirring at room temperature for 24h. Hydrothermal treatment of the aged mixture was performed using a Teflon lined-autoclave in an oven maintained at crystallization temperature and time of 100oC and 2 hr respectively. The reaction product was washed and characterized using XRD, and FT-IR. 2.3 Functionalization of synthesised zeolite A: 10-2M HMTA was prepared and mix with 50g of prepared zeolite A. This mixture was stirred at room temperature for 4hrs at 300rpm before separating the zeolite A from the mixture by filtration; it was then washed using distilled water and dried in the oven at 100oC for 12hrs. Fourier Transform Infrared Spectroscopy (FTIR) was used to confirm the functionalization. 2.4 Adsorption studies: Batch technique was employed in evaluating the rate and equilibrium data because of its simplicity. Equilibrium isotherms were obtained by studying the adsorption process at different initial dye concentration, pH, temperature and adsorbent dosage. The effect of pH was observed by varying the pH from 2- 8 and that of temperature at 303,313 and 323K, in order to evaluate the adsorption thermodynamics parameters. Effects of adsorbent dosage were also studied at 0.5, 1, 1.5 &2g/l. All these were done on methylene blue at a constant temperature of 303K except those studies in which temperatures were studied and pH of 7 except those studies in which pH were studied. The solution pH was adjusted with NaOH and HCl with the aid of a pH meter. The final concentration was estimated at maximum wavelength 662nm corresponding to maximum absorbance for MB using JENWAY UV- spectrophotometer. 3 Results and discussion: 3.1. The characterization of adsorbents: the raw kaolin, the UFZA and FZA were characterized using XRF, XRD, SEM, FT-IR, and presented elsewhere (Kovo, 2011). The results of XRF of raw and refined Ahoko kaolin are shown in Table 1 to demonstrate the refinement carried out. The table shows that the raw Ahoko kaolin contains 79.08% of SiO2 but after refining, it reduces to 60.96%. The XRD results for both UFZA & FZA as shown in Figures 2 & 3 revealed several peaks depicting minerals like quartz, mica, calcium and iron which are not unusual (Eva, 2001). The SEM of UFZA (not shown) also showed uneven platelets with low porosity but after functionalization with HMTA, uneven platelets with

voids were shown. Table 1 X-Ray Fluorescence Analysis of raw and refined Ahoko kaolin Elemental composition, % Sample SiO2 Al2O3 Na2O K2O Fe2O3 TiO2 MgO MnO Raw Ahoko kaolin 79.08 17.148 0.023 0.5 1.065 1.588 0.113 0.005 Refined Ahoko kaolin 60.958 33.832 0.12 0.602 1.871 1.469 0.191 0.002 Figure 2. XRD pattern of synthesised ZA Figure 3. XRD pattern of FZA 3.2. The FT-IR spectra: The FT-IR spectra of both synthesised and functionalized zeolite A Figure 4. FT-IR of synthesised zeolite A Figure 5. FT-IR of functionalized zeolite A were done in the range of (500- 4000) cm-1 and (500- 4500) cm-1 respectively to study theeffect of cationic surfactant on the zeolite A as shown in Figures 4 & 5. It can be deduced that the peaks shown at (423.31 and 1438.94) cm-1 in Figure 2a and (433.03 and 1440.87) cm1 in Figure 2b are as a result of symmetric stretching vibrations of SiO 4 and adsorbed water in the zeolite (Korkua and Prasetyoko, 2006). The drastic decrease in the peak of the bands is as a result severity of the cationic treatment on the zeolite A as observed at peak 2353.2cm-1 .This is also an indication of vibration stretching of CH3 group of HMTA (Zhaohui, 2005). 3.3Effect of pH on adsorption of MB One of the most important variables that influence adsorption studies is pH. It does not only influence the surface charge of the adsorbent but also the degree of ionization of the present material in the solution, the dissociation of the functional groups on the active sites of the adsorbent and also the chemistry of the dye solution (Crini, 2008,and Nandi, 2009). The effect of pH was investigated on adsorption of MB on both UFZA and FZA as shown in the Figure 6 (range of 2- 8, initial concentration of 100mg/L, temperature of 30oC and adsorbent dosage of 2g/L). From the figure, it was observed that the adsorption of MB increases with increasing pH as reported in previous work (Tsai, 2005 and Wang, 2005). This is because the optimum pH as frequently reported is 7 (Nandi, 2005) and at a lower pH, the zeolite A surface acquires positive charge resulting to electrostatic repulsion between the cationic dye molecules and zeolite A. In addition, the surface of zeolite A is more negative at higher pH leading to the increase in adsorption capacity of MB (Ho, 1999)]. 3.4Effect of initial concentration on adsorption of MB From Figures 7 and 8, it is evident that the adsorption of methylene blue onto unfunctionalized and functionalized zeolite A increases with increase in initial concentration and contact time. This is consistent with the earlier reports (Gunasekar, 2013, Hameed, 2008, Ponnusami, 2008 and Ponnusami, 2009). It was also noticed that the rate of uptake increases gradually until equilibrium were attained before decreases at 90mins of contact time due to continuous decrease in the concentration driving force (Tsai, 2005). The equilibrium adsorption capacity was achieved at 60mins for both unfunctionalized and functionalized zeolite A. However, it is obvious that the adsorption rate was higher in functionalized zeolite A than unfunctionalized one. This is because; the functionalized one has a larger surface area than unfunctionalized one as shown in BET analyses. Although, the adsorption rate is not as high as expected, which might be attributed to the fact that the used zeolite A was being locally synthesised in FUT Minna, Chemical Engineering laboratory.

3.5 Effect of Adsorbent dosage on adsorption of MB The effects of adsorbent dosage of UFZA and FZA on adsorption of MB were also investigated as shown in Figures 11 and 12. It could be deduced that the uptake of dye decreases as the adsorbent dosage increases for both UFZA and FZA. This is as a result of increment of fraction of active sites which are saturated with dye at smaller adsorbent dosages (Gunasekar, 2013 and Ho, 1999). It is also evident that the rate of adsorption increases with contact time and was more rapid at adsorbent dosage of 0.5g which is considered to be the critical dose, after which the adsorption rate decreases with increases in adsorbent dosage. This was reported in previous work (Tehran- Bagha, 2011) and can be attributed to the splitting effect of concentration gradient between the adsorbent and adsorbate (Nandi, 2009). Figure 6. Effect of pH on adsorption of MB Figure 7. Kinetics of MB unto UFZA unto UFZA & FZA Figure 8. Kinetics of MB unto FZA Figure 9. Effect of temperature on adsorption of MB unto UFZA at pH=7
$ $-# 1 1-# % %-# * $ 1$ *$ '$ ($ Jt$mgKg% &ime$min% %$$mg 1#$mg 1$$mg #$mg $ $-# 1 1-# % %-# * $ 1$ *$ '$ ($ Jt $mgKg% &ime $min% #$+ &$+ *$+ $ $-$% $-$& $-$' $-$) $-1 $-1% $ # 1$ Jt $mgKg%

p< BAo> Ao> $ $-# 1 1-# % %-# * *-# $ 1$ *$ '$ ($ Jt $mgKg% &ime$min% %$$mg 1#$mg 1$$mg #$mg

Figure10.Effect of temperature on adsorption Figure 11.Effect of adsorbent dosage on Of MB unto FZA (pH=7, D= 2g/L) adsorption of MB unto UFZA at pH=7 3.6 Effect of temperature on adsorption of MB The effect of temperature was also studied on the adsorption of MB onto UFZA and FZA at temperatures of 30oC, 40oC & 50oC while other parameters were kept constant. These are represented in Figures 9 & 10. As could be seen, the uptake of dyes increases with increasing temperature but decreases with contact time. This is also reported in previous reports (Gupta, 2003 and Shiau, 2004). The increase of dye uptake with temperature rise can be attributed to the increase in the Figure 12. Effect of adsorbent dosage on Figure 13. Linearized plot of Langmuir Adsorption of MB unto FZA(pH=7,D=2g/L) Isothermal model mobility of the dye molecules as the temperature rises, thus, producing a swelling effect within the internal structure of zeolite A which enables large dye molecules to penetrate further (Acemioglu, 2004). This is a clear indication of chemisorptions mechanism for adsorption of MB by UFZA & FZA (Tsai, 2005) .
$ 1 % * & # ' $ 1$ *$ '$ ($ Jt $mgKg% &ime $min% %g 1-#g 1g $-#g y = #$-$&(3 + $-(&#% 4R = $-(#1' y = #-&$()3 +

1-%*)& 4R = $-"**% $ $-# 1 1-# % %-# $ $-$% $-$& (KJe $gKmg% (KCe$.Kmg% BAo> Ao> .inear (BAo>) .inear (Ao>) $ $-# 1 1-# % %-# * $ 1$ *$ '$ ($ Je $mgKg% &ime $min% #$+ &$+ *$+ $ 1 % * & # ' " $ 1$ *$ '$ ($ Jt $mgKg% &ime $min% %g 1-#g 1g $-#g

3.7Adsorption isotherms The equilibrium relationship between the adsorbent and adsorbates were also evaluated by adsorption isotherms. There are several isotherm models used in analysing the experimental data and equilibrium of adsorption. Langmuir, Freundlich, and Temkin equations were tested in this work and their equations are stated below;
_ __

=
_ __

_ ____

(1) log __ = log__ +

_ _

_____ (2) __ = _____ + _____ (3) _i_ _, _ =

Y_ Z[

. Where __ is the amount adsorbed at equilibrium (mg/g), __ is the equilibrium concentration of the adsorbate (mg/L), _7 \ b are the Langmuir constant related to the maximum adsorption capacity (mg/g) and energy of adsorption (L/mg),__ is the Freundlich constant,
6 (N) is the absolute temperature, 4 is the uniGersal gas constant ()-*1&MEmolN)-

The plots of 1/qe vs 1/Ce, log qe vs log Ce and qe vs ln Ce are shown in the Figures 13,14,&15; Figure 14. Linearized Freundlich plot Figure 15. Linearized Temkins plot The values of qm, ka, kf, 1/n, AT, B1, & R2 were evaluated from the slopes and intercepts of the plots and are tabulated as shown in the table 2; From the table, it could be deduced that Table 2. Adsorption isotherm parameters UFZA FZA Langmuir qm (mg/g) 1.058 0.8075 KL (L/mg) 0.019 4.368 R2 0.952 0.7332 Freundlich
y = $-%$)13 F $-%"'' 4R = $-))1* y = $-$*)(3 + $-#)(& 4R = $-)#%# $ $-1 $-% $-* $-& $-# $-' $-" $-) $-( $%&' Je $mgKg% ln Ce BAo> Ao> .inear (BAo>) .inear (Ao>) y = $-*%)3 F $-)*$1 4R = $-)'*(

y = $-$&((3 F $-%1&* 4R = $-)#(% F$-*# F$-* F$-%# F$-% F$-1# F$-1 F$-$# $ $1%* log Je log Ce BAo> Ao> .inear (BAo>) .inear (Ao>)

Kf (L/g) 0.148 0.611 1/n 0.328 0.050 R2 0.864 0.859 Temkins AT(L/mg) 0.265 0.039 B1 0.208 R2 0.881 0.853 Langmuir is more suitable because it has highest value of R2 and for the FZA which has the lowest R2 simply indicated that the UFZA is better than FZA in all cases. 3.8 Adsorption kinetics In order to investigate the mechanism of sorption, the characteristic constant of adsorption were evaluated using pseudo- first order equation of Lagengren and pseudo- second order kinetic models and their equations are stated below; log]__ V _) l =
_ __

V
+, F-E$E ) _% _

1 (4) =
+*__* + _ __

1 (5) Where k1 (1/min) is the Lagergren rate constant of adsorption, k2 is the pseudo second order rate constant in (g/mg.min). The linear plot of log (qe- qt) vs time and t/qt vs time are shown elsewhere. The values of k1, k2, R2, & qe were evaluated from the slopes and

intercepts of the plots and are tabulated as shown in the Table 3; Table 3. Adsorption kinetics values of MB on UFZA & FZA at 30oC, pH 7 and 200 rpm agitation speed
?seudo first order ?seudo second order BAo> Ao> BAo> Ao> 0ye
-m.&/0

N1

(1Emin)

4% N1

(1Emin)

4% Je N% (gEmg min) 4% Je N% (gEmg min) 4% #$ $-$$& $-1%" $-$$& $-#*# $-%(& F*-(&' $-)1' $-"&1 $-&&1 $-((& 1$$ $-$$% $-'"$ $-$$1 $-#%' $-"#& $-))) 1-$$ $-"'$ %-%)( 1-$$ 1#$ $-$$% $-#** $-$$1 $-&(& $-"') 1-1($ $-((( $-"'( %-&($ $-((( %$$ $-$$% $-&() $-$$1 $-&'" $-")& 1-1%# $-((( $-")( %-$*) $-(((

From the table above, it is evident that the sorption of MB onto UFZA and FZA conform to pseudo- second order kinetics. 4.0 Conclusion In this study, zeolite A was synthesised from Ahoko kaolin, characterized and functionalized for adsorption studies of MB. The result showed that zeolite A can be locally synthesised and functionalized with cationic surfactant for removal of MB. The adsorption of MB unto UFZA & FZA increases with increase in pH, temperature, initial concentration while it decreases with adsorbent dosage. Isothermal models indicated that a Langmuir model is most suitable and it conforms to pseudo- second order kinetics. References Acemioglu, B., (2004). Adsorption of congo red from aqueous solution onto calcium- rich fly ash. J. Colloid Interface Sci. 273, 371.(129) Arami, M., Limaee, N.Y., Mahmood, N.M., Investigation on the adsorption capability of egg shell membrane towards model textiles dyes, chemosphere 65, 1999- 2008.(11) Aydin, H., Bulut, Y.C., (2008). Removal of copper (II) from aqeous solution by adsorption onto low cost adsorbents. J. Environ. Manag, 87, 37-45.(12) Bingol, D., Tekin, N., Alkan, M., (2010). Brilliant yellow dye adsorption onto sepiolite using a full factorial design. Appl. Clay sci., 50, 315- 321.(13) Crini, G., Badot, M., (2008). Application of chitosan, a natural aminopoly saccharide, for dye removal from aqueous solutions by adsorption processes using batch studies; a review of recent literature, Prog, Polym. Sci. 33, p. 399- 447. (124) Eva Mako, R.L.F., Janos Kristof and Erzsebet Horvath, (2001). The effect of quartz content on the mechanochemical activation of kaolinite; Journal of Colloid and interface Science. 244: pg. 359- 364.(98) Gupta, S.S, Bhattacharya, K.G, (2005). Interaction of metal ions with clays: I.A case study

with Pb (II). Application of clay science,30, Lahaye, J. (1998). The chemistry of carbon surfaces. Fuel, 77(6), 543547. (6) Gunasekar, V., and Ponnusami, V., (2013). Kinetics, Equilibrium, and Thermodynamic Studies on Adsorption of Methylene blue by Carbonized plant leaf powder. Journal of chemistry, p. 1-6 (119) Gupta, V.K., Suhas, A., Mohan, D., (2003). Equilibrium uptake and sorption dynamics for the removal of a basic dye (basic red) using low cost adsorbents. J. Colloid Interface Sci. 265,257.(128) Hameed, B.H., (2008). Equilibrium and kinetics studies of methyl violet sorption by agricultural waste. Journal of Hazardous Materials, vol. 154, no. 1-3, p. 204-212.(118) Ho, Y.S., and Mckay, G., (1999). A kinetic study of dye sorption by biosorbent waste product pith. Resources, Conservation and Recycling, vol. 25, no. 3-4,p.171-193.(121) Kovo A.S. (2011), Development of zeolites and zeolite membranes from Nigerian Ahoko Kaolin, A PhD thesis submitted to the University of Manchester UK Korkua, O., Lebda, R., Skubiszewska, J.Z., Vrublevska, T., Gunko, V.M., Ryezkowski, M., (2006). Chemical properties of natural zeolites, clinoptilolite and mordenite. Microporous, Mesoporous Mater. 87, 243.(114) M. Ghoreishi and R .Haghighi, (2003). Chemical catalytic rxn and biological oxidation for treatment of non biodegradable textile effluent. Chemical engineering journal 95163169(2) Nandi, B.K., Goswani, A., Purkuit, M.K., (2009). Adsorption characteristics of brilliant green dye on kaolin. J. Hazard Mater. 161. P.387-395.(123) Nandi, B.K., Goswani, A., Purkuit, M.K., (2009). Removal of cationic dyes from aqueous solutions by kaolin; kinetic and equilibrium studies, Appl. Clay Sci. 42, p. 583- 590. Nigam P, Armour, G., Banet, I.M., Singh, D., Marchant, R., (2000). Physical removal of textiles dyes and solid state fermentation of dye- adsorbed agricultural residues, Bioresour. Technology 72, 219- 226.(1) Ponnusami, V., Vikram, S., and Srivastava, S.N., (2008). Guava (Psidium guajava) leaf powder: novel adsorbent for removal of methylene blue from aqueous solutions, Journal of Hazardous Materials, vol. 152, no. 1, p. 276-286. Ponnusami, V., Vikram, S., and Srivastava, S.N., (2009). Kinetics of methylene blue removal from aqueous solution using gulmohar (Delonix regia) plant leaf powder; multivariate regression analysis, Journal of Hazardous Materials, vol. 169, no. 1-3, p. 119-127 Prasetyoko, D., Ramli, Z., Endud, S., Hamdan, H., Sulikowski, B., Conversion of rice husk ash to zeolite beta. Waste management, in Press.(113) Robinson, T., McMullan, B., Chandran, R. & Nigam, O. (2002). Effect of pretreatments of three waste residues, wheat straw, corncobs and barley husks on dye adsorption. Bioresour. Technol., 85, 119124 (7) Shiau, C.Y., Pan, C.C., (2004). Adsorption of Basic dyes fromaqueous solution by various adsorbents. Sep. Sci. Technol. 39 (8), 1733. (127) Tehran- Bagha, A.R., Nikkar, H., Mahmood, N.M., Markazzi, M., & Menger, F.M., (2011). The sorption of cationic dyes onto kaolin; kinetics, isotherm and thermodynamic studies. Elsevier, Georgia, 266, p.274-280 (122).

T., Robinson, G, McMullen, R. Marchant, P. Nigem, (2001). Remediation of dyes in textile effluent: a critical review on current treatment technologies with a proposed alternative, bio resource technology, 99, 247-255 (3) Tsai, W.T., Chang, Y.M., Lai, C.W., Lo, C.C., (2005). Adsorption of methyl violet dye in aqueous solution by regenerated spent bleaching earth. Journal Colloid Interface Sci. P. 289 & 333. (120) Turan, M., Mart, U., Yukstel, B., Celik, M.S, (2005). Lead removal in fixed bed columns by zeolite and sepiolite. Chemosphere 60, 1487- 1492.(11) Wang, S., Li, H., (2005). Dye adsorption on unburned carbon; kinetics & equilibrium. J. Hazard Mater. 125 (1-3), p. 71. Y., Fu and Tviraghavan, (2001). Fungal delocalization of dye waste waters a review, bioresource technology, 79, p. 251-262(4) Zhaohui, L., Gallus, L., (2005). Surface configuration of sorbed hexadecyltrimethyl ammonium on kaolinite as indicated by surfactant and counterion sorption, cation desorption and FT-IR- colloids surface, A. 264, 61.(115)

P-19 Batch Studies on Removal of Chromium from Aqueous Solution using Modified Nigeria Ahoko Kaolin
S.I. Ayilaraa; A.S. Kovoa;Abubakar, Gb and Akuso, S.Ab aDepartment of Chemical Engineering, Federal University of Technology, Minna bNational Research Institute For Chemical Technology,Zaria Abstract This study investigates the removal of chromium from aqueous solution using modified Nigeria Ahoko Kaolin. The adsorbent was intercalated with phosphate for effective removal. The study was carried out in batch mode to determine the effect of different factors such as pH of the adsorbate, concentration of the adsorbate, time, and adsorbent dose. The results showed that kaolin intercalated with phosphate iseffective adsorbent in chromium removal from aqueous solution.The adsorption data fitted into Langmuir,Freundlich,Temkin and Dubinin-Radushkevich isotherms,of which Freundlich Isotherm had the highest coefficient of determination to be 0.9839,hence gave the best fit(all followed the non-linear pattern of representation). Generally, Nigeria Ahoko Kaolin can be utilized as potential adsorbent. Keywords:Adsorbent,adsorbate,adsorption,intercalation 1. Introduction One of the most important problems of environmental contamination at present is the existence of heavy metals owed to their toxicity and cumulative properties.Due to their high toxicity for living organisms which include human beings,heavy metals are widely distributed in the environment and are ecologically important (Volesky, 2001)

A large quantity of wastes containing chromium has been directly discharged into the environment in recent years(Wang, et al (2011).Trivalent chromium compounds are considered to be less toxic than the hexavalent compounds ,however,all forms of chromium are toxic when they exist at high levels.Chromium can be released into the environment through a large number of activities such as tannery industries,metal finishing industry,steel industry,and so on.Adsorption has become a preferred method for removal of metals from aqueous solution due to its simplicity,ease in handling,availability of various adsorbents and more efficiently in the removal of heavy metals at lower concentration as compared to other technologies such as reverse osmosis,chemical precipitation,ion exchange,solvent extraction, and so on(Abbas,et al(2010).Although,different works have been reported on the modification of kaolin but no work has been done in the use of Nigeria Ahoko kaolin for chromium removal.The aim of this study was to study the removal of chromium from aqueous solution using modified Ahoko kaolin in batch mode.This was carried out though modification of the Ahoko kaolin by potassium dihydrogen phosphate and the evaluation of the adsorption equilibrium data using the equilibrium adsorption data such as Freundlich,Langmuir,Temkin and Dubinin-Radushkevich isotherms. 2.Materials and Methods Kaolin used for this experiment was gotten from Ahoko,Kogi State.The raw samples were initially analyzed by X-ray Diffraction (XRD),Scanning Electron Microscope(SEM) and X-ray Fluorescence(XRF) and thereafter refined following developed elsewhere and the results have been presented (Kovo, 2011). Modification of the adsorbent. The sample was modified to improve its adsorption capacity.100g of the clay sample were evenly balanced with 2L of 200mg/L of potassium dihydrogen phosphate(KH2PO4) in a water bath shaker for 24hrs.The samples were then washed three different times with a portion of 1L doubly distilled water to ensure complete removal of excess H2PO4- ions.The clay was then dried in the oven at a temperature of 373K. The unfunctionalized kaolin was found to have a Brunauer-Emmett-Taller (BET) surface area of 2.42980.0014m2/g while the functionalized kaolin was 16.17160.03323m2/g. Experiment Batch adsorption studies were carried out at a constant temperature of 27oC.The experiment were run in 250ml beakers usingwater bath shaker at 150rpm.Only one parameter was changed at a

particular time while all others remained constant.The adsorbate pHs were adjusted with 1M HCL of 1M NaOH just before the required amount of adsorbent were added.This was then placed in the water bath shaker for complete reaction to take place.The stirring was kept constant duringthe experiment.The beakers were withdrawn from the shaker at the predetermined time interval and the supernatant was separated by filtration using filter paper.The final concentrations were then analyzed by AAS. The percentage removal of chromium from the aqueous solution was calculated using (1) Where Cinitial is the initial metal ion concentration and Cfinal is the final metal ion concentration and the uptake of metal at equilibrium time was calculated using (2) Where qe is the amount of adsorbed chromium in mg/g,Co and Ce are the initial and equilibrium metal ion concentration in mg/l,v is the volume of the aqueous solution in ml and w is the weight of the adsorbent in g. Effect of pH of the adsorbate was carried out by adding 0.4g of both phosphates functionalized and unfunctionalized samples in 100ml of 40ppm aqueous solution of chromium.This was agitated for 2hrs with variation of pH from 2.0 to 6.0.The effect of time was also investigated by adding 0.4g of both phosphate functionalized and unfunctionalized samples in 100ml of 40ppm aqueous solution of chromium which was agitated for interaction time of 30,45,60,90 and 120mins at an optimum pH of 6.00.2.So also was the effect of adsorbate dose which was investigated through addition of 100ml of 40ppm aqueous solution of chromium and was varied with doses of both functionalized and unfunctionalized clay samples of 0.2,0.3,0.4,0.5 and 0.6g.The samples were agitated for 2hrs at an optimum pH of 6.00.2.For the effect of concentration of the adsorbate,0.4g of both phosphate functionalized and unfunctionalized samples were varied with adsorbate concentration of 40,50,60,70 and 80mg/L, agitated for an optimum time of 2hrs at an optimum pH of 6.00.2 Results and Discussion Chromium Adsorption
$ 1$ %$ *$ &$ #$ '$ "$ )$ ($ %*&#'

7 adsorption(unfunction aliKed) 7 adsorption(functionali Ked)

$ %$ &$ '$ )$ 1$$ *$ &# '$ ($ 1%$ 7 adsorption( unfunctiona liKed) 7 adsorption( functionaliK ed) "$ "% "& "' ") )$ )% $-% $-* $-& $-# $-' 7 adsorption (functional iKed$ 7 adsorption (unfunctio naliKed)

% adsorption ``pH Figure1: Effect of pH on adsorption of chromium on functionalized and un-functionalized kaolin The effect of pH on adsorption of chromium on functionalized and unfunctionalized kaolin is presented in figure 1. pH is an important parameter in metal adsorption because it affects the degree of ionization of the adsorbate.Changes in the effect of pH takes place as a result of the type of adsorbent usedits behavior in the solution and the type of ions adsorbed.For the functionalized kaolin,the removal efficiency increases throughout with increase in pH .Increase in the removal efficiency occur to a pH of 4 for the un-functionalized,reduces at pH of 5 and later increased at the pH of 6.The highest removal efficiency occurred at a pH of 6 with a value of 84.1%
3 adsorption

Time

Figure 2: Effect of time on adsorption of chromium metal on functionalized and unfunctionalized kaolin The effect of time on adsorption of chromium on both functionalized and un-functionalized kaolin is presented in figure 2. It was observed that instant adsorption took place at the initial stage in both cases.A gradual decrease in the adsorption process was observed in both cases,this is because of the time required for the equilibrium to be attained.The maximum adsorption of chromium by the functionalized kaolin was 77.1% in 30mins and 75.14% in the un-functionalized one. In both cases, equilibrium can be attained after some time or can occur almost immediately at 30mins.This shows that high removal efficiency of chromium a short period of 30mins. % adsorption
$ %$ &$ '$ )$ 1$$ &$ #$ '$ "$ )$ 7adsorptio n(functiona liKed) 7 adsorption( unfunction aliKed)

Adsorbent dose Figure 3: Effect of adsorbent dose on adsorption of chromium metal on functionalized and un-functionalized kaolin The effect of adsorbent dose on adsorption of chromium in both functionalized and unfunctionalized kaolin is presented in figure 3. The optimum adsorption of chromium occurred at a dosage of 0.4g in both cases with 80.4% in the functionalized and 77.6% in the unfunctionalized.This implies that 0.4g of the adsorbent is the optimum that can be used in chromium removal.
3 adsorption

Concentration Figure 4: Effect of concentration of adsorbate on adsorption of chromium on functionalized and un-functionalized kaolin The effect of concentration of adsorbate on adsorption of chromium in both functionalized and unfunctionalized

kaolin is presented in figure 4. The maximum adsorption efficiency obtained was at 60mg/l in both cases and decreases with increase in the concentration of the adsorbate. Hence, the % adsorption of chromium is dependent on the initial concentration Equilibrium Study Langmuir,Freundlich,Temkin and Dubinin-Radushkevich equilibrium isotherms were used to correlate the experimental equilibrium adsorption data Langmuir Isotherm Figure 5:Non-linear plot of Langmuir Isotherm This is usually used to describe adsorption of solute from a liquid solution and it is perhaps the best of all the isotherms which describes adsorption.This isotherm assumes that adsorption takes place at specific homogenous sites within the adsorbent.It can be represented as (3) This can be linearized as (4) Where Ce is the equilibrium concentration of the adsorbate in mg/L qe is the amount of metal adsorbed per gram of the adsorbent at equilibrium in mg/g Qo is the maximum monolayer coverage capacity in mg/g KL is the Langmuir isotherm constant in L/mg The values of Qo and KL were gotten from the slope and intercept of the Langmuir plot of 1/qe against 1/Ce.The Langmuir isotherm essential features can be expressed in terms of equilibrium parameter RL which is a dimensionless constant referred to as equilibrium parameter or separation factor. It can be expressed as (5) Where Co is the initial concentration KL is a constant which is related to the energy of adsorption RL signifies the adsorption nature which can be unfavourable if RL>1,linear if RL=1,favourable if 0<RL<1 and irreversible if RL=0 As calculated from the data,Qo which is the maximum monolayer coverage capacity was found to be 20.66mg/g,KL which is the Langmuir Isotherm constant was found to be 0.16L/mg,RL which is the separation factor was found as found to be 0.16L/mg, RL which is the separation factor was found to 0.12.Since RL was greater than zero but less than one,it implies that Langmuir Isotherm is favourable.Also,the coefficient of determination R2 was found to be 0.217 for the linear plot of Langmuir.This lower coefficient of determination suggests that it is not appropriate to use this type
$ $-$# $-1 $-1#

$ $-1 $-% (KJe (KCe

.angmuir Isotherm studies of eJuilibrium

5eries1 ?oly(5eries1)

of linearization; hence a non-linear plot gave a better value of 0.9815.This means it follows the non linear form of the isotherm. Freundlich Isotherm Figure 6:Non-linear plot of Freundlich Isotherm This isotherm is usually used in describing a heterogeneous surface of the adsorption characteristics(Hutson,2000).Itis represented as (6) Where Kf is the Freundlich Isotherm constant in mg/g Qe is the amount of metal adsorbed per gramof the adsorbent at equilibrium in mg/g Ce is the equilibrium concentration of the adsorbate in mg/L n is the adsorption intensity This can be linearized as (7) A plot of logQe against log Ce gave a slope of 1/n and logKf as intercept Kf, a constant represents an approximate indicator of adsorption capacity while 1/n represents a function of the strength of adsorption in the adsorption process.The smaller the 1/n,the greater the expected heterogeneity which reduces to a linear adsorption isotherm when 1/n=1.If n is between 1 and 10;it implies a favourable sorption process (Goldberg,2005).From the linear plot,1/n was found to be 4.19 which indicate that Freundlich Isotherm is also favourable.The coefficient of determination R2 was determined to be 0.1078.This follows the same pattern as the Langmuir that is the lower coefficient of determination makes it inappropriate to use this type of linearization.R2 for non-linearized plot was found to be 0.9839; this proves that the adsorption data fitted well to Freundlich Isotherm model but in a non-linearized form.
$ $-# 1 1-# $ $-# 1 1-# log Je logCe

!reundli"h Isotherm #tudies of eJuilibrium

.og+e ?oly(.og+e) ?oly(.og+e)

Temkin Isotherm Figure 7: Non-linear plot of Temkin Isotherm This isotherm has a factor that considers the interactions of adsorbent-adsorbate.This model assumes that the heat of adsorption of all molecules in the layer decreases linearly,(Aharoni et al, (1977) rather than logarithmic with coverage.Constants were determined from the slope and intercept by plotting qe(quantity adsorbed) against ln Ce.It is given as (8) Where AT is Temkin Isotherm equilibrium binding constant in L/g bT is the Temkin Isotherm constant R is the universal gas constant(8.314J/molK) T is temperature at 300K B is a constant related to heat of sorption in J/mol The linear plot for Temkin Isotherm gave a much lower value of coefficient of determination,R2=0.0475 as compared to 0.9825 for its non- linear plot,this higher value makes it a more appropriate way of using a non-linearization form of representation. AT was found to be
$ 1$ %$ $1%* Je lnCe

&em;in Isotherm #tudies of EJuilibrium

Oe ?oly- (Oe)

2.01L/g while B was found be 3.53J/mol, indicating that the heat of sorption is a physical adsorption process. Dubinin-Radushkevich Isotherm Figure 8: Non-linear plot of Dubinin-Radushkevich Isotherm The isotherm stated that the characteristic sorption curve is related to the porous structure of the sorbent.It is expressed as (9) It can be written in linear form as lnqe= lnqD BD(RT(ln(1+1/Ce))2 (10) ED is the apparent energy and can be computed using (11)

From the linear plot qD was determined to be 18.1966mg/g,the mean free energy,E is a parameter used for predicting the type of adsorption<8KJ/mol indicates physical adsorption process.(Itodo, et al, (2009) E was found to be 0.97KJ/mol which signifies a physisorption process.R2 for the linear plot was found to be 0.1302 while the non-linear plot was 0.9787;the non linear plot gave a better representation of the model. Table1: Langmuir Isotherm constants for the adsorption of chromium unto modified kaolin
$ % & $ $-% $-& l n J e ln$(L(KCe%2

Dubinin16adush;evi"h Isotherm studies of eJuilibrium

lnJe ?oly- (lnJe)

Metal ion Cr 1/n n KF R2 0.2384 4.19 7.50 linear 0.1078 Table 2: Freundlich Isotherm constants for the adsorption of chromium unto modified kaolin Table 3: Temkin Isotherm constants for the adsorption of Chromium unto modified kaolin Metal ion Cr AT(L /mg) bT B R2 2.01 706.8 3.53 linear 0.0475 Nonlinear 0.9825 Table4:Dubinin-Radushkevich Isotherm constants for the adsorption of chromium unto modified kaolin Met

al ion Cr qD(mg/ g) BD(mol2 /KJ2) E(KJ/ mol) R2 18.199 6 5.3510

-7

0.97 line ar 0.13 02 Non line ar 0.97 87 Conclusion The results of this study show that modifying kaolin with phosphate is very effective in removal of chromium from aqueous solution.It also shows that pH of the adsorbate,concentration of the adsorbate,contact time,and adsorbent dose are highly responsible for chromium removal from aqueous solution.The mechanism of adsorption unto kaolin was deduced to be physical adsorption process.The adsorption data fitted into Langmuir,Freundlich,Temkin and Dubinin-Radushkevich Isotherms,but Freundlich adsorption Isotherm was found to have the highest coefficient of determination, hence gave the best fit. They all follow the non-linear pattern of the model. ` Nonlinear 0.9837 Metal ion Cr Qo(mg /g) KL(L/ mg) RL R2 20.66 0.16 0.12 Linear 0.21 71 Nonlinear

0.98 15 References 1. Abbas M.M.A;Farooq M;and Ilyas Z;Kinetics of activated chemisorption Part 2,Theoretical models,J.Chem 2. C.Aharoni, M.Ungarish, Removal of chromium(III) ions from aqueous solution by natural clays, Middle-East Journal of Scientific Research 6(4), 377-381(2010).Soc.Faraday Trans.73(1977) 456-464 3. El-Shafey,E.I.(2007).Sorption of Cd(II) and Se(IV) from aqueous solution using modified rice husk,.Journal of Hazardous Materials,147(1-2),546-555). 4. S.Goldberg, Equations and Models Describing Adsorption Processes in Soils Soil Science Society of America,677S,Chemical Processes in Soils, Book Series(2005) no.8 5. N.D.Hutson and R.T.Yang,Adsorption,J.Colloid interfSci(2000)pp 189 6. Itodo A.U,Happiness U.O,Obaroh I.O,Usman A,Audu S.S.Temkin,R-D,Langmuir and Freundlich adsorption Isotherms of industrial dye uptake unto H3PO4 catalyzed poultry waste bio adsorbent,Journal of Science and Technology research 2009b;8(1):52-56 7. A.S. Kovo, Development of Zeolites and Zeolites Membrane from Ahoko Nigerian Kaolin, PhD Thesis submitted to the University of Manchester, UK , 2011 8.B.Volesky,Detoxification of metal bearing effluents:Biosorption for the next century,Hydrometallurgy 59(2001) 203-216
.

P-20 STRATEGY FOR BALANCING PETROLEUM INDUSTRY ACITIVITIES AND

BIODIVERSITY CONSERVATION: AN ASSESSMENT OF BIODIVERSITY EXPLOITATION IN THE STUBBS CREEK FOREST RESERVE, AKWA IBOM STATE, NIGERIA.

Joshua T. Ndoho Federal Ministry of Environment, Department of Forestry, Abuja. E-mail: timndoho@yahoo.com Abstract Industrial activities in petroleum industry have been associated with enormous environmental degradation and social crises. Therefore, in the fast changing world, the petroleum industry should embrace biodiversity conservation with a view to mainstreaming it in the sector. The paper which makes use of data collected by the author between 2005 and 2009 in Stubbs Creek Forest Reserve (SCFR) examines the importance of SCFR, ecologically and economically. Primary and secondary data collected have been utilized to present data on the study area, aspects of exploitation of biodiversity in the SCFR with the agent of deforestation identified to include petroleum industrialists. Trend in biodiversity loss was determined using satellite imageries of 1976 and 2005. Petroleum industry has contributed to erosion of biodiversity in SCFR; as Mobil Producing Nigeria Unlimited, Frontier Oil Limited, Network Production and Exploration Nigeria and Universal Energy Resources Limited activities have affected the conservation of biodiversity in the SCFR. The paper concludes that SCFR is a production base for oil companies, therefore an institutional and policy framework should be put in place to fund and actualize Biodiversity Action Plan (BAP) in SCFR. When this and other measures of ensuring multiple use forest management are put in place, there will be a balancing of petroleum industry activities and biodiversity conservation in the SCFR. Introduction It is axiomatic that petroleum resources sustain the Nigerian economy. However, industrial

activities in the sector have been associated with enormous environmental degradation and social crises. Petroleum industrial activities pose various threats to sustainable development in the Niger Delta, where the bulk of Nigerians petroleum resources concentrate. The environmental consequences of oil industry activities in Nigeria have received the attention of several researchers in the past. The works of Awobanyo (1981); Famuyiwa (1998); Eromosele (1998); Chukwu et al (1998); Grevy (1995); Olomo and Omene (1995); NDES (1997); Onosode (2003); Orubu et al (2004); and Ndoho and Inah (2008) are some of the few in this connection. Petroleum exploration and production activities are carried out in designated oil concession areas duly leased out to the various companies. Therefore, in the fast changing world, the petroleum industry should embrace biodiversity conservation. Man and animals enjoy a host of ecological services rendered by forests. Forests filter and purify water and air. They also conserve soil and prevent erosion hazards. They are also homes for biodiversity and helps man to experience and execute his nature. Destruction of forests by man means destroying the ecosystem. The Nigerian government has recognized the need to conserve its biological resources and has made a commitment to conserve 25% of Nigerias total land area (Federal Ministry of Environment, 2003). The biodiversity of any country is its heritage over which it exercises sovereignty and the right of ownership, management and use. Biodiversity is very basic for human life as well as the life support systems. The World Conservation Strategy regards biodiversity as the foundation which biotechnology develops. Tropical forests have a special role in the conservation of biodiversity. The Stubbs Creek Forest Reserve (SCFR) , an evergreen wet tropical forest in the SouthSouth part of Akwa Ibom State, is a nature reserve of great importance, not only as a storehouse of numerous biological resources but also for its invaluable hydrological function. This moist tropical rain forest is generally well known for its rich biodiversity. SCFR was constituted a forest reserve in 1930 so that proper management of its rich and diverse resources could guarantee their availability and functions at all times. The Reserve is at a cross road between environmental management and economic development as noted by Attah (2003). Between 1970 and now, government has been allocating parts of the SCFR for both private and public uses. Activities of petroleum companies are now common in the Reserve. There is a need to balance petroleum industry activities and conservation of the SCFR. This paper examines biodiversity exploitation in the SCFR vis--vis petroleum industry activities with a view to mainstreaming biodiversity conservation in petroleum industry in SCFR. Method The study made use of primary and secondary data. The primary data were collected between 2005 and 2009 using questionnaire, semi-structured interview schedules, direct observations, field measurements, taking of photographs, participatory rural appraisal (PRA) and GIS analysis of satellite imageries. Sources of secondary data included journals, proceedings of conferences, Environmental Impact Assessment (EIA) reports, and numerous published and unpublished work on the subject matter. Descriptive statistics such as mean and percentage are used in presenting the data. Study Area The Stubbs Creek Forest Reserve is located at the southern end of Akwa Ibom State of Nigeria. It stretches from Ibeno through Enwang and James Town. The SCFR forms a buffer zone between the Atlantic Coast and the Akwa Ibom State mainland. It is located between the Atlantic

Ocean in the South, the Qua Iboe Terminal of Mobil Producing Nigeria Unlimited (MPNU) in the West, the Cross River Estuary in the East and the Stubbs and Widdenham Creeks in the North. The SCFR lies approximately between longitudes 7o54IE and 8o18IE and latitudes 4o32IN and 4o38IN. Its original area was 311km2 (120 miles) in 1955 (E.R.L.N., 1955). Estimated area in 1998 was 161.15km2(AKSEPA, 1998). The primary Local Government Areas (L.G.As) around the SCFR that exploit the SCFR are Esit Eket, Eket, Ibeno and Mbo L.G.As. The SCFR is the first and only gazette mangrove forest in Nigeria. Faunal species such as Sclaters guenon (Cercopithecus sclateri), which is endemic to Nigeria, the red mangabay (Cercopithecus torquatus), the spotty nosed monkey (Cercopithecus nictitans), mona monkey (Cercopithecus mona), bush buck (Tragelapus sripus) bush pigs (Potamochoerus procus) and elephant (Loxodonta africana) as well as monitor lizards, alligators, short snorted crocodiles, tortoise and turtles were once abundant with numerous species of birds. Some of these species have been extirpated due to intensive poaching, hunting and destruction of their natural habitats. For example, the forest elephant, leopard, manatee and hippopotamus are either very rare or no more part of the SCFR. Many primates and reptiles, particularly the Sclaters guenon and the short snorted crocodiles are now seriously endangered. The vegetation has also been heavily destroyed through petroleum industry activities, uncontrolled and non-selective timber exploitation, bush clearing through fires, palm wine tapping, fire wood extraction and other unsustainable activities. Thus, the Reserve which was once rich in commercially important species, is now characterized by logged over naturally regenerating forest with scattered farmlands. Species of plants with important economic values are seriously threatened because of unsustainable exploitation of biodiversity and land use activities in the Reserve. The petroleum industry has impacted on the SCFR by the activities of Mobil Producing Nigeria Unlimited and Marginal oil field operators such as Universal Energy Resources Limited, Frontier Oil Limited and Network Exploration and Production Nigeria. In this direction, Petroleum Industry took more than 179,000 hectares of the Reserve between 1970 and 2005. Results and Discussion Exploitation of biodiversity in the SCFR is currently at unsustainable rate. There is a growing market demand for biological resources from SCFR because of increasing population and rising cost of living occasioned by the thriving oil industry in the area. SCFR stands today as logged over forest denuded of most economic trees and highly degraded. Large proportion of the habitat in the SCFR has been seriously disturbed. Land use in the forest could best be described as having marginal oil fields, a complex mosaic of farms, abandoned farmlands, regenerating forest, secondary forest, palm bush, seasonally flooded forest, swamp forest and mangrove. Result Deforestation And Exploitation Of Biodiversity In SCFR Unsustainable exploitation of biodiversity in SCFR has affected the flora and fauna in the forest. Agents of deforestation in the Stubbs Creek Forest Reserve were identified. These are presented in Table 1. The Table reveals that timber exploitation is the first known agents of deforestation in the SCFR. Petroleum industrialist and farmers closely followed the timber exploiters as agents of deforestation in the SCFR. Table 1: Assessment of agents of deforestation by foresters and enlightened stakeholders around SCFR
S/N Agents Assessment of frequency of contribution to deforestation (N=120)

Mean Very High (5) High (4) Moderate (3) Low (2) Very Low (2)

1 Farmers (Slash and Burn) 70 29 15 4 2 4.34 2 Loggers (Timber Exploiters) 75 26 12 6 1 4.4 3 Commercial Firewood Exploiters 65 32 17 2 4 4.23 4 Petroleum Industrialists 67 38 8 3 4 4.34 5 Palm wine Tappers, and Local Gin Distillers 20 23 54 17 6 3.28 6 Infrastructural Developing (Road Construction, etc) 29 45 33 9 4 3.27 7 Plantain Developers 15 40 45 15 5 3.38 Source: Authors Fieldwork (2007) Exploitation of biodiversity in SCFR is both for sustenance and income generation. Resources of varying quantity and economic values are extracted continuously from the forests. Table 2 presents quantity and economic value of some important biological resources exploited from SCFR in 2006. Table 2: Quantity and Economic value of some important biological resources in SCFR in 2007 S/N Resources Unit of Collection/Sale Season of Collection Frequency of Collection Quantity Collected per Trip/week Total per Season Average Cost per Unit N Total Cost per Season N Ranking
1 Timber Logs Dry (Nov.-Mar.)

Wet (Apr.-May) Weekly 25 700 5500 3850000 1st 2 Firewood Bundles Dry (Nov-Mar) Wet (April-July) Daily 5days/week 15 2700 450 121500 2nd 3 Palm Oil 20 Litres plastic Container Dry (Nov-Mar) Wet (April-July) Weekly 4 128 1300 166400 10th 4 Kernel 25kg Bag Dry (Nov-Mar) Wet (April-July) Weekly 2 64 600 38400 14th 5 Periwinkle 25kg Bag All Weekly 5 160 550 88000 13th 6 Local Gin (Kai-Kai) 20 Litres plastic Container All Weekly 6 312 3400 1060800 3rd 7 Palm Wine 20 Litres plastic Container All Daily (7days a week) 2 730 500 365000 8th 8 Bush Meat Number Wet (Apr.-Oct) Weekly 7 364 2500 910000 4th 9 Fish Baskets/Basins Dry (Nov.-Feb.) Wet (Mar.-June) Daily (6days a week) 2 168 3500 588000 5th 10 Prawns Baskets/Basins Dry (Nov-Mar) Wet (April-July) Daily (6days a week) 3 576 700 403200 7th 11 Afang (Gnetum spp) Bundles All Daily (5days a week) 15 2700 120 32400 9th 12 Chewing Stick Bundles All Daily (5days a week) 10 2600 200 520000 6th 13 Parrots Number All Monthly 20 240 550 132000 11th 14 Rattan Bundles Dry (Nov-Mar) Wet (April-July)

Monthly 20 720 130 129600 12th

Source: Authors Field Work (2007) Trend in Biodiversity Loss in SCFR The trend in biodiversity lost was determined from 1970 to 2009 using original estimated area of 310.8km2 in 1970 and surveyed area data in 1998 of 161km2 documented in AKSEPA (1998). This is presented in Table 3. Based on this projection, between 1970 and 2008 (28 years), the average rate of loss of the forest was 5.32km2 per year. This projection shows that by 2009 ending, 68.69% of the original 310.8km2 had been lost and that in about 18 years after 2009, all the biodiversity in SCFR would have been eroded. Table 3 indicates the projected forest cover of SCFR from 1970 to 2009 using original estimated area in 1970, measured area in 1998 and satellite imagery of 2005 projected area from 1970 to 2009. Table 3: Projected forest cover of SCFR from 1970 to 2009 using original estimated area in 1970, measured area in 1998 and satellite imagery of 2005 projected area from 1970 to 2009 Year Projected remaining forest reserve area (km 2) Projection based on measured area in 1998 Projection based on satellite imagery of 2005 projected to 2009 1970 310.8 310.8 1974 284.05 287.5 1979 257.3 263.5 1984 230.55 239.85 1989 2003.8 216.2 1994 177.55 192.55 1999 150.8 168.91 2004 124.05 145.25 2009 97.3 121.6
Total forest cover lost from 1970 to 2009

213.5 189.2 Source: Authors fieldwork and analyses Satellite imageries analyses using GIS application has shown that core forest with fewer disturbances was about 12.56km2 in 2005 while disturbed forest was 56.6km2 making a total of 69.16km2 of the actual forest in 2005. This actual forest are constantly being exploited and with the rate of deforestation estimated at 4.73, this remaining forest shall be lost completely by about 2024. Table 4 shows the lost in forest cover based on satellite imageries analysis. Based on the analyses of the Satellite Imageries of 1976 and 2005, the remaining forest area in 2005 was about 145.41km2. The lost in forest cover area between 1976 and 2005 was 165.59km 2. The data of satellite imageries analysis is summarized in Table 4. Table 4: Land cover change pattern in SCFR between 1976 and 2005 from satellite imageries analysis using GIS. Forest cover type/percentage of each type

Area of Coverage Change in Cover 1976 2005 Type (km2) Less disturbed (Primary) forest 65.42 12.56 -52.86 Disturbed (Secondary) Forest 13.83 56.6 -42.77 Highly exploited/Deforested forest 66.16 76.25 -10.09 Percentage of primary forest in SCFR 44.99 8.6 Percentage of Secondary forest in SCFR 9.51 38.92 Percentage of Highly exploited/Deforested 45.50 52.44 Source: Authors field work with GIS application in 2009. Threats to Conservation of Biodiversity in SCFR Threats to conservation of biodiversity in SCFR include deforestation, habitat loss and fragmentation, chemical pollution and petroleum production causing gas flaring, industrial discharges, release of effluent and oil spills. The professional foresters as well as some enlightened stakeholders believe that the threats to biodiversity conservation in SCFR are complicated by the presence of petroleum industry in the area. They attributed other threats to the existence of petroleum industry in the area. Table 5 shows the perception of threats to biodiversity before oil production (pre-1970) and during oil production (post-1970) era in the SCFR. Table 5 indicates that all the threats were perceived to be higher during oil production era than before oil production started. Table 5: Threats to biodiversity conservation before and during oil production era
S/N Threats Higher before oil production (pre-1970) Higher during oil production (post- 1970)

Yes % No % Yes % No %

1 Cultivation of farmland 15 12.5 105 87.5 110 91.7 10 8.3 2 Hunting of animals 40 33 8 66.7 105 87.5 15 12.5 3 Kai-kai (Local gin) distillation 12 10 108 90 112 93.3 8 6.7 4 Fragmentation into farms, roads, etc 9 7.5 11 92.5 115 95.8 5 4.2 5 Industrialization activities 4 3.3 116 96.7 116 96.7 4 3.3 6 Chemical Pollution 5 4.2 115 95.8 118 98.3 2 1.7 7 Palm wine tapping 25 20.8 95 79.2 98 81.7 22 18.3 8 Selling of trees for timber 13 10.8 107 89.2 104 86.7 16 13.3 9 Exploitation of non-timber forest products 45 37.5 75 62.5 88 73.3 32 26.7 10 Presence of new species (Nypa palms, etc) 20 16.7 100 83.3 112 93.3 80 6.7 11 Urbanization activities 13 10.8 107 89.2 114 95 6 5 12 Migration of people into SCFR Area 25 20.8 95 79.2 88.3 88.3 14 11.7 Source: Authors fieldwork (2007) This could be true as SCFR adjoins almost the entire on-shore mining lease area of Mobil Producing Nigeria Unlimited (MPNU) who was allocated 100 hectares at inception and 200 hectares in 1977 for QIT expansion is an indication of the fact that petroleum industry and conservation of SCFR needs a balance. Furthermore, Uquo Marginal Field in OML 13, Stubbs Creek Marginal Field in OML 14, among other foot prints of the petroleum industry have impacted on the biodiversity conservation in SCFR. Discussion

Deforestation in SCFR is a serious problem as it is driven by complex agents and causes that have been embedded in the unsustainable exploitation of biodiversity. This position agrees with Ruddel (1994), Burgess (1992), Repetto and Gillis (1997), World Bank (1995), among others. Oil exploitation activities that were carried out before1970s and the on-going oil production activities such as clearing of seismic lines in the forest destroyed the forest and also opened up the area for unsustainable exploitation as seen in the presence of Universal Energy in OML 14 covering 42km2 in SCFR and Frontier Oil Limited in OML 14, Mobil Producing Nigeria Unlimited QIT at Mkpanak, among others. Oil production has threatened biodiversity conservation in the area that Mobil Producing Nigeria Unlimited (MPNU) has built its Qua Iboe Terminal (QIT), constructed a culverted road through the swamp connecting the QIT to Ibeno and Eket, which have contributed to habitat loss and fragmentation. The petroleum industry has therefore constituted a virile a source of threats to the conservation of biodiversity. This observation has been corroborated by Olagbende (1977); Ogbe (2003), Terbough (1992), Amin (2002) and Attah (2003). SCFR management is now faced with the increasingly complex challenge of reconciling the demands of various users. The way forward is to embrace sustainable forest management practices as a conservation strategy capable of enhancing poverty alleviation. Balancing Petroleum Industry and Conservation is achievable by the use of multiple use forest management which will promote a compromise between environment and the varied uses of the SCFR. (Ndoho and Inah, 2008). It is possible that the economic, social and environmental objectives can be achieved through a multiple-use approach, if the rural people who live close to the forest resources are directly involved in the management as observed by Pootchil (1986). The author advocates that the state should not be blinded by the huge economic gains she makes from economic and industrial project such as petroleum production to suffer imminent future ecological services. Strategies for balancing Petroleum Industry Activities and Biodiversity Conservation It has been established that SCFR is a basic life supporting system currently providing for the various needs of the oil companies concerned and the people. The conservation of biodiversity in a way capable of improving biological, social and economic components with the intention of improving the well-being of the land, biota and people shall be invaluable. This calls for biodiversity mainstreaming. Biodiversity mainstreaming is the integration of biodiversity concerns into policies of all the petroleum companies operation in and around the SCFR. Mainstreaming systematically takes into consideration environmental issues as early as possible in the decision-making process where decisions can best benefit from environmental opportunities and avoid negative impacts on the environment. In this way, mainstreaming can help align policies, programmes and operations with the long-term requirements of sustainable development, help modernize development policy content and procedures, and promote a pro-active approach rather than responding to impacts as they unfold. The most productive strategy to be adopted in balancing petroleum industry activities and biodiversity conservation in SCFR is to maintain in situ conservation. For this to be possible, the stakeholders (Petroleum companies in the area, Federal Government, State Government, Local Governments and representatives of the communities) have to come together and adopt the following approaches: i. Re-gazzething SCFR as Stubbs Creek Conservation Area (SSCA) and establish Stubbs Creek Conservation Area Management Board (SCCAMB). ii. Establishment of Stubbs Creek Sanctuary (SCS). SCS should be located within the Stubbs Creek Buffer Zone which shall include a section of Atlantic Ocean Beach. The buffer zones should include

all areas south of Stubbs and Winddenham Creek to the Atlantic Ocean, west to the MPNU boundary and east to Okposso and the Cross River Estuary. iii. Multiple-use forest management approach should be integrated into the Biodiversity Action Plan (BAP) for the SSCA. Conclusion It appears impossible to conserve SCFR without exploitation of the resources as the forest is providing base subsistence to the local people surrounding the forest. It is also a production base for some oil companies. This calls for working out a compromise by examining possibilities of developing land management systems with biological, social and economic components with the intention of improving the well-being of the land, biota and people which is currently lacking. Therefore, Biodiversity Action Plan (BAP) is strongly needed for SCFR. The Federal Ministry of Environment and Akwa Ibom State Ministry of Environment and Mineral Resources should provide policy and Institutional framework which should bring all Oil Companies and others associated with oil and gas industry in the area together to fund and actualize Biodiversity Action Plan in SCFR. This will inhibit the imminent eclipse of the SCFR which is currently appearing to be in its twilight years. When this and other measures of ensuring multiple use forest management are put in place, there will be a balancing of petroleum industry activities and conservation of biodiversity in SCFR. References AKSEPA (1998). The Stubbs Creek Conservation Project (SSCP) Akwa Ibom State, Management Plan, Akwa Ibom State Environmental Protection Agency (AKSEPA), Uyo. Amin, M. N. (2002). Biodiversity and Floristic Composition of Sundarbans in Bangladesh EnviroNews, (Newsletter of ISWB, India), Vol. 8, No. 4, October 2002. Attah, V. I. (2003). Problems of Sustainability of the Stubbs Creek Forest Reserve, Akwa Ibom State, Nigeria, Journal of Nigerian Environmental Society. Awobanjo, S. A. (1981). Oil Spillage in Nigeria 1970-1080, Paper Presented at the 1981 International Seminar on Oil Industry, Lagos, NNPC. Burgess, J. C. (1992). Economic Analysis of the Causes of Tropical Deforestation , Discussion Paper No. 92-03. London: London: Environmental Economic Centre. Chukwu, L. O., Brown, C. O. and Nwankwo, D. I. (1998). The Impact of Oil pollution in the hydrochemistry and biota of the tidal Creeks and Canals in Ondo State, 9 th International Conference on the Petroleum Industry and the Nigerian Environment, Abuja, 538-576. Eastern Region Gazette, Nigeria (1955). Gazette No. 52 0f 27th October, 1955. Eromosele, V. E. (1998). Costing Niger Deltas Oil Spills: A Joint Stakeholders approach, 9 th International Conference on the Petroleum Industry and the Nigerian Environment, Abuja, 358-368. Famuyiwa, B. A. (1998). Seabed Survey of the Impact of Oil Based Drilling Fluid System on Offshore Environment, 9th International Conference on Petroleum Industry and the Nigerian Environment. Federal Ministry of Environment (2003). National Biodiversity Strategy and Action Plan. Abuja, Federal Ministry of Environment. Grevy, P. (1995). The Niger Delta, Nigeria Draft: Pollution Assessment Study Submitted to the World Bank. Niger Delta Environmental Survey (NDES) (1997). Environmental and Socio-economic Characteristics, Phase 1 Report, Port Harcourt.

Ndoho, J. T. and Inah, O. (2008). Petroleum Industry and Conservation of Biodiversity in the Niger Delta A Paradigm for Action. Proceedings of 2008 50th Annual Conference of Association of Nigerian Geographers (ANG), Department of Geography and Regional Planning, Universality of Calabar, Calabar: Index Books Publishers Limited. Ogbe, M. G. (2003) Biodiversity and the Oil Industry in the Niger Delta A Sensitive Environment. Journal of Nigerian Environmental Society, 1 (1), 95-112. Olagbende, O. T. (1977). Oil Exploration, Production and Environmental Management in Nigeria. Proceedings of the 25th Annual Conference of the Forestry Association of Nigeria, Ibadan: Forestry Association of Nigeria. Onosode, G. (2003). Environmental Issues and the Challenges of the Niger Delta. Perspectives for the Niger Delta Environmental Survey Process, Lagos: CIBN Press. Orubu, C. O., Fajingbesi, A., Odusola, A. and Magbagbeola, N. (2004). Environmental Regulations in the Nigerian Petroleum Industry: Compliance Status of Compliance and Implications Sustainable Development, Research Report, ACBF/NCEMA, Ibadan. Pootchil, I. (1986). Rural Development and Development Countries. An Interdisciplinary Introductory Approach. Guelph, Ont. Rapetto, R. and Gillis, M. (1997). Public Policies and the Misuse of Forest Resources. Cambridge: Cambridge University Press. Ruddel, T. (1994). Population, Development and Tropical Deforestation: a Cross National Study: In Katrina and David W. Pearce (Eds) The causes of Tropical Deforestation (pp 96-105). Vancouver: UBC Press. Terbough, J. T. (1992). Maintenance of Diversity in Tropical Forests. Biotropica, 24 (2b), 283-292. World Bank (1995). Defining An Environmental Development Strategy for the Niger Delta, Vol. II, Washington DC.

P-21 Effect of Particle Size and Temperature Variation on the Yield of Essential Oil from lemon grass using Steam Distillation
aE.T.Akhihiero

and b*B.V.Ayodele aDepartment of Chemical Engineering, Delta State University, Oleh Campuss. b Department of Chemical Engineering, University of Benin, Benin City. Nigeria Abstract A large number of herb materials contain essential oils with extensive bioactivities. Acknowledging the importance of plants and their medicinal value, extraction of essential oil had been carried out using steam distillation method. In this study steam distillation was used to extract oil from lemon grass leaves. Steam distillation method was found to be one of the promising techniques for the extraction of essential oil from plants as reputable distillers use this technique to preserve the original qualities of the plant oil. The distillation was conducted in Clevenger apparatus in which boiling, condensing and decantation was done. The result shows there was progressive increase of the essential oil yield from 0.51 to 0.84 as the particle size increases from 4mm to 20mm. Similarly, the oil yield increased from 0.45 to 0.75 as temperature increases from 10 to 50oC. *Corresponding author Keywords: Particle sizes, Lemon grass, Temperature, Extraction, Essential Oil. 1.0 Introduction Essential oils contain highly volatile substances that are isolated by a physical method or process from plants of a single botanical species [1,2]. The oils normally bear the name of the plant species from which they are derived. Essential oils are so termed as they are believed to

represent the very essence of odor and flavor. Essential oil plants and culinary herbs include a broad range of plant species that are used for their aromatic value as flavorings in foods and beverages and as fragrances in pharmaceutical and industrial products. Essential oils derive from aromatic plants of many genera distributed worldwide. Oils are used in the embalming process, in medicine and in purification rituals. There are also over 200 references to aromatics, incense and ointments in the old and new testaments. Research has confirmed centuries of practical use of essential oils, and we now know that the 'fragrant pharmacy' contains compounds with an extremely broad range of biochemical effects. There are about three hundred essential oils in general use today by professional practitioners. Continual bombardment of viral, bacterial, parasitic and fungal contamination occurs in our body. Essential oils are a great benefit to help protect our bodies and homes from this onslaught of pathogens. Immune system needs support and these essential oils can give the required endorsement. [ 13,14] Plant oils and extracts have been used for a wide variety of purposes for many thousands of years (Jones 1996). These purposes vary from the use of rosewood and cedar wood in perfumery, to flavoring drinks with lime, fennel or juniper berry oil, and the application of lemongrass oil for the preservation of stored food crops. In particular, the antimicrobial activity of plant oils and extracts has formed the basis of many applications, including raw and processed food preservation, pharmaceuticals, alternative medicine and natural therapies. Since ancient times, herbs and their essential oils have been known for their varying degrees of antimicrobial activity. More recently, medicinal plant extracts were developed and proposed for use in food as natural antimicrobials. Steam distillation is used in the extraction of essential oil from the plant material. It is a special type of distillation or a separation process for temperature sensitive materials like oils, resins, hydrocarbons, etc. which are insoluble in water and may decompose at their boiling point. The fundamental nature of steam distillation is that it enables a compound or mixture of compounds to be distilled at a temperature substantially below that of the boiling point(s) of the individual constituent(s). Essential oil contains components with boiling points up to 200C or higher temperatures. In the presence of steam or boiling water, however, these substances are volatilized at a temperature close to 100C, at atmospheric pressure. [2] Analysis of essential oil is done by using gas chromatography with mass spectrometer. The qualitative and quantitative analysis is done to know the constituents in the oil and the percentage of components present in the oil respectively, by doing so we can know the purity of that particular oil. [3]

2.0 Preparation of raw material

The leaves which was obtain from the junior staff quarters of the university of benin, was washed to remove all the dirt. The washed leaves were divided into two parts. One part was left to dry for two days under ambient temperature and the other part was allowed to dry for about 20 minutes in order to dry off the water from the surface. The leaves were then chopped to a size of 2cm.

2.1 Experimental Setup:

The schematic diagram of experimental setup is Figure 1. The experiment was conducted in a Clevengers apparatus. Apparatus consist of one round bottom flask of 1000ml which is connected with another two way round flask which holds raw material. The top flask is connected with condenser through the connecter. The separating funnel is used for the separation of essential oil and water. Figure1: Experimental set up for extraction of essential from lemon grass by steam distillation

2.2 Experimental Procedure

Fresh leaves were cut into pieces less than 2 X 2 cm within half a day after collection and 150200 g boiled with 500 ml of distilled water in a Clevenger apparatus until oil distillation ceased after 5-6 hours. The volume of essential oils was determined from a calibrated trap. The essential oils in the distillate were dried over anhydrous Na2SO4 and kept in the freezer.

3.0 Results and Discussion

In this study, the effect of the particle size, temperature and time on the yield of essential oil from lemon grass (Cymbopogon citratus) were studied. Four experiments were conducted and the yield of the oil obtained was calculated from the relationship between the essential oil mass obtained and the raw material mass used in the extraction process. The yield of essential oil obtained varies with the particle size of the lemon grass at different time of heating. The essential oil yield variation along with particle sizes at different time of heating is shown in Figure 2. It was observed that the highest values of 0.54, 0.55, 0.58, 0.69, 0.7 essential oil yields were recorded at particle sizes of 4mm, 8mm, 10mm, 15mm and 20mm, at varying time of 30, 60, 90 and 120 minutes respectively. While the lowest values of 0.45, 0.49, 0.51, 0.53 and 0.56 were obtained from the same particles sizes. However, the highest value of lemon grass essential oil was obtain from particle size of 20mm. This trend could be explained in term of the surface area of the lemon grass. Lemon grass with larger particle size having larger surface area would give higher yield of essential oil than lemon grass with smaller surface area. This agreed with the findings of [10] which explained that the changes of the mean particle size have a relevant effect on the extraction yield. For further studies, optimization of the process variables could be carried out to determine optimum yields This studies only reveals that changes in process variables such as particle size, extraction temperature and time have relevant effect on extraction yield. A progressive increase in the essential oil yield was observed as the particle size increases from 4mm to 20mm. The pressures required for extraction at these conditions were 0.15 and 0.14 MPa, respectively. In the process of size reduction to obtain crushed bean, there is a substantial fibre destruction coupled with breaking of oil cells, all of which facilitate the increase in the yield. Figure 2: Effect of particle size on the yield of essential oil at different time Figure 3: Effect of temperature on the yield of essential oil at different particle size The effect of temperature on the yield of essential oil obtained from lemon grass is shown in Figure 3. There was an increase in the oil yield from 0.53 to 0.75 when the temperature was 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 5 10 15 20 25 Essential oil yield Particle Size (mm) Yield of essential oil at 30mins Yield of essential oil at 60mins

Yield of essential oil at 90mins Yield of essential oil at 120mins 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 $ 1$ %$ *$ &$ #$ '$ Essential oil yield Temperature oC Yield of Essential oil at 4mm Yield of Essential oil at 8mm Yield of Essential oil at 10mm Yield of essential oil at 15mm increased from 10 to 50oC respectively. This observation can be explained from the fact that the heat and the steam generated at 50oC has more rupture effect on the cell structure of the leaves thus allowing the release of more essential oil at that temperature. This is in agreement with the findings of [13] which study the effect of temperature on the yield of essential of from chamomile varieties. Conclusion From this study, it was revealed that particle size, heating temperature and distillation time had influence on oil yield, during steam distillation lemon grass. Therefore, these process conditions must be carefully controlled during the extraction process. These conditions would greatly help in carryout detail process design and scale up for the commercial scale extraction of essential oil from lemon grass. References 1. Adam,R.P. (2010) Identification of essential oil components by gas chromatography/quadrupole mass spectroscopy. 3rd ed. Allured Publishing, Carol Stream, IL. 2001, p 456. Barden A, Anak NA, Mulliken T, Song M. Hearth of the Matter: Agarwood use and trade and CITES implementation for Aquilaria malaccensis, Traffic Network Report 19982000. TRAFFIC International, Cambridge, UK, pp 151. 2. Bhuiyan, M.N.I, Begum, J., Bhuiyan, M.N.H.(2009) Analysis of essential oil of eaglewood tree (Aqulilaria agallocha Roxb.) by gas chromatography mass spectrometry. Bangladesh J Pharmacol. 4: 2428. 3. Cassel,E., Vargas, R.M.F., Martinez, N., Lorenzo, D., Dellacessa, E.(2009) Steam distillation modeling for essential oil extraction process. Ind Crop Prod. 29: 171-76. 4. Chalchat, J.C,, Garry, R.P., and Michet, A. (1997) Variation of the chemical composition of essential oil of Mentha piperita L. during the growing time. Journal of Essential Oil Research 9: 463465. 5. Demirbas, A. (2001) Supercritical Fluid Extraction and Chemicals from Biomass With Supercritical Fluid, Energy Conversion and Management, (42) , pp. 279294. 6. Zhiyi, L. Xuewu, L. Shuhua, C. Xiaodong, Z. Yuanjing, X. Yong, W. and Feng, X. (2006) An Experimental and Simulating Study of Supercritical CO 2 Extraction for Pepper Oil, Chemical Engineering and Processing, 45, pp. 264267. 7. Yang, Y. Gharaibeh, A. Hawthorne, S. B. and Miller, D. J.(1995). Combined

Temperature & Modifier Effects on Supercritical CO2 Extraction Efficiencies of Polycyclic Aromatic Hydrocarbons from Environmental Samples, Analytical Chemistry, 67(3), pp. 641646. 8. Kiriamiti, H. K. Rascol, E. Marty, A. and Condoret, J. S. (2001) Extraction Rates of Oil from High Oleic Sunflower Seeds With Supercritical Carbon Dioxide, Chemical Engineering and Processing, (41), pp. 711718. 9. Kumoro, A.C, (2010). Extraction of Sarawak Black pepper Essential oil using supercritical carbondioxide. The Arabian Journal of Science and Engineering, Vol. 35 No 2B, pp 7-16 10. Rodica, V. Manuela. M, and Gainar, I. (2004) Anise Essential Oil Extraction by supercritical CO2 Analele Universitatii din Bucuresti Chimie, Anul XII (serie nou O), vol. I-II, pag. 297302 11. Alonge, A.F., Olaniyan, A.M., (2003). Effect of processing factors on oil yield of shea butter during wet extraction. Niger. J. Tech. Dev., 3(2): 126-133. 12. Ibrahim, A., Onwualu, A.P., (2005). Technologies for extraction of oil from oil bearing agricultural products: A review. J. Agric. Eng. Tech., 13: 58-70.

P-22 KINETICS AND ISOTHERM STUDIES OF Pb(II) ADSORPTION ON IKPOBA CLAY

*Uwadiae, S. E.1, Aluyor, E.O.2, Okieimen, C.O3 and Oboh, I.O.4 1Department of Chemical Engineering, Igbinedion University, Okada, Edo state, Nigeria 2,3,4 Department of Chemical Engineering ,University of Benin, Benin City, Edo state, Nigeria
4Department

of Chemical and Petroleum Engineering ,University of Uyo, Akwa-Ibom state

Corresponding author* email: suwadiae@yahoo.com

.

ABSTRACT The sorption of lead (II) ions from aqueous solution onto Ikpoba clay has been studied. The study investigated the effect of varying contact time, solution pH, adsorbent dose and initial concentration of metal ion on sorption. Batch equilibrium and kinetic experiments were conducted at 25OC, using <0.02mm particle sizes. The kinetic and equilibrium models were fitted employing the non-linear regression method, using a trial-and-error procedure in the Microsoft Excel solver. In order to determine the best fit isotherm, five error analysis functions were used: hybrid fractional error function, Marquardts percent standard deviation, average relative error, sum of the errors squared and sum of the absolute errors. However, the sum of normalized error was further employed in order to have a better comparison between the error functions sets for the isotherm models. With the highest R2 value of 0.9887 and lowest sum of normalised error value of 0.0108, the Sips isotherm fitted the equilibrium data better than the other isotherm models. The pseudo-second order model gave the best fit to the kinetic data as it had the lowest standard error of the estimates value of 3.22*10-6 and the highest R2 values of 0.9887 for the adsorption of Pb(II) onto Ikpoba clay. 1.0 Introduction Clays have received considerable attention especially as potential adsorbents for environmental research. Deposits of this important raw material are widely distributed in Africa, especially, Nigeria (Fasuba et al., 2001; Gbadebo, 2002). The removal of heavy metals from wastewater is important in terms of protecting public

health and environment (Unlu and Ersoz, 2006). Many industrial activities such as metal plating and mining operations introduce heavy metals into the environment via their waste effluents (Srivastava et al., 2006). Precipitation, ion-exchange, phytoextraction, ultrafiltration, membrane separation and adsorption are the usual methods for the removal of heavy metal ions from aqueous solutions (Das and Kumar Jana, 2006). Due to its simplicity and easy operational conditions, adsorption is a widely-used process (Mabrouk, et al., 2009). Activated carbon has been the most employed adsorbent for heavy metal removal from aqueous solution, but it is however expensive (Okieimen, 2008). Many reports have appeared on the development of low-cost materials. These include: modified groundnut (Arachi hypogea) husks (Okieimen et al., 1991); clay (Chen and Wang, 2007); Palm kernel shell (Okieimen, 2008); Luffa cylindrica (Oboh et al., 2011). Many investigators have evaluated natural clay as a low-cost adsorbent due to its adsorption properties for heavy metals including cobalt, cadmium, zinc and chromium ions (Ceylan et al., 2005; El-Hendawy, 2009; Al-Jlil and Alsewailem, 2009). In this study, clay from Ikpoba in Edo state, Nigeria has been used as adsorbent. For the present study, the Freundlich, Langmuir, Redlich-Peterson, Sips and Radke-Prausnitz adsorption isotherms were examined for lead ion sorption onto Ikpoba clay for their ability to model the equilibrium sorption data at a fixed temperature of 25OC. Also, five different nonlinear error functions, hybrid fractional error function (HYBRID), Marquardts percent standard deviation (MPSD), average relative error (ARE), sum of the errors squared (ERRSQ) and sum of the absolute errors (EABS), were examined and in each case the isotherm parameters were determined by minimising the respective error function across the concentration range studied using the solver add-in with Microsofts spreadsheet, Excel .The kinetic data were fitted to Pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion models. 2.0 Materials and Methods 2.1 Collection of samples Clay samples were collected from the clay deposits at Ikpoba river in Benin; and at depths of up to 10 cm with the aid of a plastic shovel and digger and hand-picked to minimize the possibility of contamination. About 2.0 kg of sample was collected and placed in small polythene bag and then dried at 100oC for 24 hour, pulverized and sieved to geometric mean size of <0.02 mm before analysis. 2.2 Preparation of aqueous solution The salt used for the preparation of the aqueous solutions was analytical grade Lead (II) Nitrate. Other chemicals used were: sodium hydroxide and trioxonitrate (V) acid. All reagents used were of analytical grade. Stock solutions of 1000mg/l each of Pb(II) was prepared by dissolving reagent grade PbNO3 in appropriate quantity of distilled water. Distilled water was used for preparing stock solutions and dilution. 2.3. Characterization of Ikpoba clay The specific surface area of Ikpoba clay was determined from the Brunauer, Emmett and Teller (BET) multipoint method (Bruanuer et al., 1938) and the pore size distribution were obtained using Barret, Joyner, and Halenda (BJH) method (Barret et al., 1951). This was carried out by N2 adsorption using Micromeritics instrument (Tristar 3000). Also pore volume was determined using the surface area analyzer which utilizes the BET theory for the

analysis and plots of each sample data and then presents the results of pore volume (cm3/g). The cation exchange capacity (CEC) of clay was determined by the procedure described by Chapman (1965). Also, X-ray Spectrometer (model PW 4030) was used to determine the chemical composition of the clay. 2.4. Batch adsorption experiment Adsorption was performed in batch experiments where 50 mL of aqueous solutions of Pb(II) were mixed with 0.6g of adsorbent (size <0.02mm) in conical flasks. The pH of each suspension was adjusted in the range, 3-12 by adding HNO3 or NaOH aqueous solutions and monitored with pH meter (Suntex, model SP-701).The mixed solutions were shaken in optima mechanical shaker (model 08-752) at 300 rpm and 25oC for a given time. After the contact time was completed, solution and clay were separated by filtering through a filter paper (Whatmann no. 42). The residual metallic ion concentrations were determined using an Atomic Absorption Spectrophotometer (Buck scientific, model 210 VGP). Adsorption mechanisms were determined according to the predefined procedure with Pb(II) concentrations ranging from 20 to 60 mg l1. A duplicate was analyzed for every sample to track experimental error and show capability of reproducing results (Marshall and Champagne, 1995). The adsorbate uptake, q (mg/g) was calculated as: _ = _______x
_

(1) Where q is the specific uptake in mg/g at equilibrium, Co and Ce are the initial and final concentration in mg/l, respectively, V the volume in litres of aqueous solution and m is the mass of adsorbent in grams. The aqueous samples were taken to preset time intervals and the concentrations of metal ions were similarly measured. The amount of adsorption at time t, qt (mg/g), was calculated by: __ = ______x
_

(2) Where: Ct (mg/l) is the concentrations of aqueous solution at any time t. 2.5 Kinetic and equilibrium studies The kinetic equations considered are: pseudo first-order (Largegren, 1898), pseudo-second order (Ho and Mckay, 1999), Elovich (Ayoob et al., 2008) and intra-particle diffusion model (Weber Jr and Morris, 1963).The equations of the kinetic models are given in Table 1 Table 1: Kinetic adsorption models Kinetic Model Equation Pseudo first-order (Largegren, 1898) __ = ___1 V ____V_____ (3) Pseudo-second order (Ho and Mckay, 1999) __ = ____
__

_______

(4) Elovich (Ayoob et al., 2008) __ = _ _ _ _! x Y_ + _ _ _ ___ (5) Intra-particle diffusion (Weber Jr. and Morris, 1963) __ = _[y_ + \ (6)

In addition to using coefficient of determination (R2), the models were evaluated by standard error of the estimates, SEE which measures the point by point differences of the amount of the divalent metal ions taken up by the adsorbent predicted by the models and the actual q measured experimentally:
](( = )r+_,,-_E$__,,1E%*_
&_#

(7) The isotherm equations considered are: Langmuir (Langmuir, 1918), Freundlich (Freundlich, 1906), Sips (Sips, 1948) and Redlich-Peterson (Redlich and Peterson, 1959). The equations of the isotherm models are given in Table 2 Table 2: Equilibrium isotherm models Isotherm Equation Langmuir (Langmuir,1918) __ = "-E)(Hh_
__(Hh_

(8) Freundlich (Freundlich, 1906) __ = U=\_ _P& (9) Sips (Sips,1948) __ = "-E)($h_
_P` __($h_

(10) Redlich-Peterson (Redlich and Peterson, 1959 ) __ =

_P`

(,h_

__>Hh_

(11) 2.5.1 Validity of adsorption isotherm- error functions A trial-and-error was used for nonlinear regression to minimize or maximize the objective function using the solver add-in function, Microsoft Excel, Microsoft Corporation. The models parameters were evaluated by some error functions, namely HYBRID, MPSD, ERRSQ, ARE and EABS. Contrary to the linearization models, nonlinear regression usually involves the minimization of error distribution (between the experimental data and the predicted isotherm) based on its convergence criteria (Kumar et al., 2008). As each of the error criteria is likely to produce a different set of isotherm parameters, an overall optimum parameter set is difficult to identify directly. Hence, in order to try to make a meaningful comparison between the parameter sets, a procedure of normalizing and combining the error results was adopted producing a so-called sum of the normalized errors for each parameter set for each isotherm (Ho et al., 2002). Below is a list of error functions used and their definitions Table 3: List of error functions Error Function Definition/Expression Reference Sum squares errors (ERRSQ) ++__,0_:A V __,=:,=*<
@

# [ <M_

Kumar and Sivanesan 2006) Hybrid fractional error

function (HYBRID)
1$$ V_ +. +__,0_:A V __,=:,=*# __,0_:A 2
< & <__

Ng, et al., 2002 Average relative error (ARE)

1$$ +; __,0_:A V __,=:,= __,0_:A ;
& <M_

Kapoor and Yang, 1989 Marquardts percent standard deviation (MPSD)

1$$ x+1 __,0_:A V __,=:,= __,0_:A ?
< [# <M_

Marquardt, 1963 Coefficient of determination (R2)

+__,0_:A V O_O_OO,=O:OO,O=*# r+__,0_:A V O_O_OO,=O:OO,O=*# + +__,0_:A V __,=:,=*# Boulinguiez et al.,2008

sum of the absolute errors (EABS)

r 4__,0_:A V __,=:,=4<
&<

Ng et al., 2003 Sum of Normalized error (SNE) 1 Karadag et al., 2007 Where __,=:,= is the equilibrium capacity obtained from the isotherm model, __-0_:A is the equilibrium capacity obtained from experiment, and O_O_O is the average of __, n is number of data points and p is number of parameters within the isotherm. 4.0 Results and Discussion Table 4: Physico-chemical properties of Ikpoba clay PARAMETERS IKPOBA CLAY
__

CEC (meq/100 g) 4.8 Specific surface area - BET (m/g) 8.6932 Average Pore Diameter Range (nm ) 26.22612 Pore Volume (cm/g) 0.101267 Table 4 shows the surface area, average pore diameter and pore volume for the adsorbent used for this study. The Specific surface area using the BET method was 8.6932m/g , the average pore diameter was 26.22612nm and pore volume was 0.101267 cm/g. As observed, the surface area for the clay is relatively low; below the range of 10 to 20 m2/g established for kaolinite (Bohn et al., 1985; Yong et al., 1992). This may be due to the high quartz content of the clay. The CEC was also observed to be low (4.8 meq/100 g). This is however within the range of values of 3 and 15 meq/100 g for Kaolinite given elsewhere (Grim, 1968). With a pore diameter of 26.22612nm, the clay sample is mesoporous based on IUPAC classification (RodriguezReinoso and Linares-Solano,1989 Table 5: Chemical composition (%) of Ikpoba clay Sample SiO2 Al2O3 Fe2O3 P2O5 MnO K2O Cr2O3 CaO TiO2 ZnO Ikpoba clay 78.65 15.17 3.49 0.62 0.02 0.27 0.01 0.14 1.57 0.06 From the XRF results in Table 5 it is seen that SiO2 had the highest composition of 78.65, Al2O3 was next with a percentage of 15.17; while the lowest oxide present was Cr2O3 with a percentage of 0.01 in the clay samples. Fig. 1: Effect of pH of solution on adsorption of Pb(II) onto Ikpoba clay (adsorbent dosage= 0.60 g, initial Pb(II) concentration 20 mg/l, contact time of 2 hrs and temperature 25 PC). Figure 1 shows increase in percentage removal of Pb(II) as pH increases from 3 to 11 and thereafter decreases. This trend in the percent removal is in agreement with researches elsewhere (Haji-Djafari et al., 1981; Zimdahl and Hassett, 1977). As reported elsewhere (Beukes et al., 2000) metal adsorption is pH-dependent and that the intensity of the phenomenon increases drastically above pH 7.0. The observed decrease beyond pH 11 may be due to the formation of soluble hydroxyl complexes. The hydrolysis of cations occurs by the replacement of metal ligands in the inner co-ordination sphere with the hydroxyl groups. This replacement occurs after the removal of the outer hydration of metal cations (Badmus , 2009).
$-$$ 1$-$$ %$-$$ *$-$$ &$-$$ #$-$$ '$-$$ "$-$$ )$-$$ $ % & ' ) 1$ 1% 1& 3 Pb 6emoval p<

Fig 2: Effect of adsorbent dosage on adsorption of Pb(II) onto Ikpoba clay: pH 11, initial Cu(II) concentration 20 mg/l, contact time 2 hrs and temperature 25OC.

Percent removal of Pb2+ ions from the aqueous solution (50 ml, pH 11) using 0.2 to 1.4g of

Ikpoba clay is shown in Fig. 2. The effect of adsorbent dosage on the uptake of Pb(II) by Ikpoba clay was studied for initial concentration of Pb(II) = 20 mg/l. It is found that the removal of Pb(II) by Ikpoba clay increases with an increase in the adsorbent dose. Increase in percentage removal of Pb(II) with the adsorbent dosage could be attributed to increase in the adsorbent surface areas, augmenting the number of adssorption sites available for adssorption, as reported elsewhere (Kumar and Porkodi, 2007). It is also found that any further addition of the adsorbent beyond 1g did not cause any significant change in the adsorption. This may be due to overlapping of adsorption sites as a result of over-crowding of adsorbent particles.
Fig 3: Effect of initial concentration on the adsorption of Pb(II) by Ikpoba clay: pH 11, adsorbent dose 0.6g, contact time 2 hrs and temperature 25OC.

Percent removal of Pb(II) from the aqueous solutions (50 ml, pH 11) in the concentration range of 10 to 60 mg/l is shown in Fig 3. The percentage removal is seen to be decreasing as concentration increases from 20 to 60 mg/l at constant adsorbent dosage level of 0.6 g. This effect can be explained as follows: with a high metal ion/adsorbent ratio increases, the higher energy sites are saturated and adsorption begins on lower energy sites, resulting in decreases in the adsorption efficiency (Zouboulis et al., 2002).
$-$$ 1$-$$ %$-$$ *$-$$ &$-$$ #$-$$ '$-$$ "$-$$ )$-$$ ($-$$ $ $-% $-& $-' $-) 1 1-% 1-& 1-' 3 6emoval of Pb$II% ions 'dsorbent dose $g% $-$$ 1$-$$ %$-$$ *$-$$ &$-$$ #$-$$ '$-$$ "$-$$ )$-$$ ($-$$ $ 1$ %$ *$ &$ #$ '$ "$ 3 6emoval of Pb$II% ions Initial metal ion "on"entration $mgKl%

Fig. 4: Time dependent study of the sorption of Pb(II) on Ikpoba clay using 0.8 g adsorbent dose.; pH 11, initial Pb(II) concentration 20 mg/l and temperature 25OC.

Fig. 4 shows the percent removal of Pb2+ ions from the aqueous solution (50 ml, pH 11) using 0.8g of Ikpoba clay as adsorbent with the contact time varied from 5 to 120 minutes at 300 rpm. It is seen that as the contact time increases from 5 to 120 minutes the percent removal of the Pb(II) also increases. By increasing the agitation time, the boundary layer resistance will be reduced and there will be an increase in the mobility of ions in the solution (Hanafiah and

Ngah, 2006). Table 6: Predicted isotherms by minimizing the error distributions using sorption onto Ikpoba clay four different error functions for lead (II)
<sotherm +onstants :4414 AB;+6<1; >4: :>@5 :445O ,Y@4<0 2?50 5;: .angmuir Oma3 &#-)1*'1 &1-1%'*# 1)*-))( 1%#-")&# 1$)-&1)# N. $-$1*( $-$1%&1 $-$1&'%( $-$$*$%* $-$$&&&" $-$$#1'& 1A $-11*# $-*(%' $-$$&"* $-11#& $-1$## Areundlich NA $-#&#*' $-#&#*)' $-##(1*" $-##*) $-##$*)" n 1-$$&(%& 1-$$&)'# 1-$1&'(( 1-$$(*)& 1-$$### $-*$() 1A $-$&1) $-1$#' $-$$#*) $-$(*) $-$'#% 5ips Oma3 1(-'')1& %1-&(1%& %*-&%"%" **-*)#11 **-#))#% )0)()Ns $-$%&&') $-$%%'(# $-$%1%)& $-$1##%" $-$1##%% n $-)&&$$% $-)#"")" $-)"*)&" $-(1#)'" $-(1(&)# 1A $-$#%( $-$)(' $-$$%(# $-$'*1 $-$'*& 4edlichF ?eterson NL $-#&&$&" $-#&*(1) $-##' $-##%$(1 $-#&(()' $-##%& . $-$$11#1 $-$$1$%% $-$$*'&# $-$$%*$1 $-$$1(1 z $-))" $-(%& $-($$''& $-(**"*) $-)"#$)% 1A $-$&1( $-1$#& $-$$&"( $-$)"% $-$'**
$-$$ 1$-$$ %$-$$ *$-$$ &$-$$ #$-$$ '$-$$ "$-$$ )$-$$ ($-$$ $ %$ &$ '$ )$ 1$$ 1%$ 1&$ 3 6emoval Conta"t &ime $min%

Table 7: Kinetic model parameters obtained using the nonlinear methods Kinetic models Parameter s Pseudo first order K1(min-1) 0 . 2054 qe(mg g1) 4.7968 R2 0.7845 SEE 0.1995

Pseudo second order K2(g mg-1min-1) 0.089 qe(mg g1) 5.0000 R2 0.9887 SEE 3.22E-06 Elovich L (gmg-1) 2.5 M(mgg-1 min) 45783.2 R2 0.6340 SEE 0.2475 Intraparticle diffusion: Kp(mgg-1min-1/2) 0.0765 C(mgg-1) 5.54 R2 0.7043 SEE 0.0574 Table 6 shows the error functions corresponding to the minimized deviations between the experimental equilibrium data and the predicted isotherms suggested. Non-linear optimization method was used to determine the isotherm model parameters as listed in Table 3. The parameters were determined by minimizing five non-linear statistics: HYBRID, MPSD, ERRSQ, ARE and EABS as described by Allen et al. (2003). Since the application of these five different error methods will produce different isotherm parameter sets, it is difficult to directly identify an overall optimum parameter set. A standard procedure normalizing and combining various errors for better and meaningful comparison between the parameter sets (for single isotherm model) was adopted resulting in a so-called sum of normalized errors (SNE) as used by researchers elsewhere (Kumar and Sivanesan, 2006; Rivas et al.,2006).This method allows a direct comparison of the scaled errors and hence identifies the isotherm parameters that would provide the closest fit to the measured data. Freundlich had the best fit to experimental data based on ARE error function with a value of 0.0416. Also, on the basis of MPSD error function, Redlich-Peterson had the best fit to experimental data with a value of 0.00633; and on the basis of EABS, ERRSQ and HYBRID error functions, Sips isotherm had the best fit to experimental data for Pb(II) adsorption onto Ikpoba clay with respective values of 0.0896, 0.00295 and 0.0631. Sum of normalized errors (SNE) was obtained and used as an indicator of which isotherm had the overall best fit to the experimental equilibrium data.Sips isotherm gave the overall best fit to experimental data for Pb(II) adsorption onto Ikpoba as it was observed to have the least SNE value of 0.0108. The R2 values obtained were 0.7845 for pseudo-first order; 0.9887 for pseudo-second order; 0.6340 Elovich; 0.7043 for intraparticle diffusion for varying initial concentrations of Pb(II) as seen in Table 7. Their respective SEE values were 0.195 for Pseudo-first order; 3.22*10-6 for Pseudo-second order; 0.2475 for Elovich and 0.0574 for Intraparticle diffusion for varying initial concentrations of Pb(II). The pseudo-second order kinetic model best fits the data as it had the lowest error value (SEE) of 3.22*10-06. The differences of the R2 and the SEE values could be clearly shown for pseudo-first-order kinetic model and intraparticle diffusion. At R2 value of 0.8614, the SEE was 0.0271,

meanwhile at R2 value of 0.7845 the SEE value was 0.1995; while at R2 value of 0.7043, the SEE value was 0.0574 for intraparticle diffusion. These results further underscore the need to consider error function values in establishing a model 4.0 Conclusions The equilibrium adsorption and kinetics of Pb(II) ions by Ikpoba clay has been reported. The adsorption of Pb(II) ions onto the Ikpoba clay is found to be dependent on the initial metal ion concentration, solution pH, adsorbent dose and contact time. The equilibrium results have been modelled and evaluated using four different isotherms, Langmuir, Freundlich, Sips and Redlich-Peterson. Non-linear optimization method was used to determine the isotherm model that best describes the data by minimizing six different error functions, ARE, EABS, ERRSQ, HYBRID, MPSD and SNE .Sips isotherm was found to best-fit the equilibrium data for adsorption of Pb(II) ions onto Ikpoba clay within the experimental range. Three kinetic models fitted were pseudo-first order, pseudo-second-order, Elovich and intraparticle diffusion. The pseudo-second order model gave the best fit to the kinetic data. References Al-Jlil, S.A. and Alsewailem, F.D., (2009). Saudi Arabian clays for lead removal in waste water. Applied clay science, 42:671-674 Allen, S.J., Gan, Q., Matthews, R., Johnson, P.A., (2003). Comparison of optimized isotherm models for basic dye adsorption by kudzu. Bioresource Tech. 88, 143-152. Ayoob, S., Gupta, A.K., Bhakat, P.B. and Bhat, V.T., (2008). Investigations on the kinetics and mechanisms of sorptive removal of fluoride from water using alumina cement granules, Chemical Engineering Journal. 140: 614. Badmus. M.O.A., (2009). Batch studies of the treatment of brewery wastewater using charred periwikle (Typanotonus fuscatus) shells. Ph.D. thesis, University of Benin, Benin City, Nigeria. Barret, E.P., Joyner, L.G., Hanlenda, P.P. (1951), The determination of pore volume and area distributions in porous substances. I: Computations from nitrogen isotherms, J. Am. Chem. Soc. 73: 373380. Beukes, J.P., Giesekke, E.W., Elliot, W., (2000). Nickel retention by goethite and hematite. Miner. Eng., 13,1573-1579. Bohn, H.L., McNeal, B.L., OConnor, G.A., (1979). Soil Chemistry. Wiley, New York. Boulinguiez, B., Le Cloirec, P., Wolbert, D., (2008). Revisiting the determination of Langmuir parameters application to tetrahydrothiophene adsorption onto activated carbon, Langmuir. 24 :64206424. Bruanuer,S., Emmett, P.H., Teller,E.,(1938). Adsorption of gases in multimolecular layers, J. Am. Chem. Soc. 60, 309316. Chapman, H.D., (1965). Cation-exchange capacity. In:C.A. Black (ed.). Methods of soil analysis - Chemical and microbiological properties. Agronomy 9:891-901. Chen, H., Wang, A.,(2007). .Kinetic and isothermal studies of lead ion adsorption onto palygorskite clay, Journal of Colloid and Interface Science 307, 309316 Ceylan, H., T. Sahan, R. Gurkan and S. Kubilay, (2005). Removal of some heavy metal cations from aqueous solution by adsorption onto natural kaolin. Adsorption Science and Technology, 23:519-534.

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